EP0001944B1 - Esters of alpha-halogenated alcohols, method of preparation and application to the synthesis of esters of alpha-cyano substituted alcohols - Google Patents

Esters of alpha-halogenated alcohols, method of preparation and application to the synthesis of esters of alpha-cyano substituted alcohols Download PDF

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Publication number
EP0001944B1
EP0001944B1 EP78400142A EP78400142A EP0001944B1 EP 0001944 B1 EP0001944 B1 EP 0001944B1 EP 78400142 A EP78400142 A EP 78400142A EP 78400142 A EP78400142 A EP 78400142A EP 0001944 B1 EP0001944 B1 EP 0001944B1
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Prior art keywords
group
formula
cyclopropane
dimethyl
cis
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German (de)
French (fr)
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EP0001944A3 (en
EP0001944A2 (en
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Jacques Martel
Jean Tessier
Jean-Pierre Demoute
André Teche
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Sanofi Aventis France
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Roussel Uclaf SA
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Priority claimed from FR7732415A external-priority patent/FR2407200A1/en
Priority claimed from FR7732414A external-priority patent/FR2424249A1/en
Priority claimed from FR7821811A external-priority patent/FR2432011A2/en
Priority claimed from FR7821812A external-priority patent/FR2432016A2/en
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C255/00—Carboxylic acid nitriles
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C43/00—Ethers; Compounds having groups, groups or groups
    • C07C43/02—Ethers
    • C07C43/20—Ethers having an ether-oxygen atom bound to a carbon atom of a six-membered aromatic ring
    • C07C43/225—Ethers having an ether-oxygen atom bound to a carbon atom of a six-membered aromatic ring containing halogen

Definitions

  • the group R 1 is derived from substituted 2-aryl 2-isopropyl acetic acids whose carbon in position 2 is an asymmetric carbon, which brings about in this group the existence of two enantiomeric forms and of a racemic.
  • the carbon carrying the substituent X is an asymmetric carbon.
  • the A isomer is the one of the two which is the most mobile in thin layer chromatography. According to certain theoretical considerations but without wishing to be bound by the accuracy of the attribution of the chiralities which we deduce therefrom, it is plausible to attribute to the isomer A, the absolute configuration (S) for the carbon carrier of the substituent X.
  • the compounds of formula I A of the invention include, for a given definition of the substituents X, R 1 and R 2 , all the compounds originating from the combination of an isomer; optically active (or racemic), resulting from the existence of the asymmetric carbon (s) of the acid part R 1 of the molecule with an optically active (or racemic) isomer corresponding to the alcoholic copula:
  • the invention particularly relates to the compounds of formula 1 comprising a group (R ') in which Y represents a hydrogen atom and Y 2 represents a group:
  • R 2 represents a group A having for value those in which X represents a fluorine atom; those in which R 2 represents a group A having for value and in which X represents a fluorine or bromine atom as well as those in which X represents a chlorine atom.
  • the subject of the invention is also a process for the preparation of the compounds of general formula I A , as defined above, a process characterized in that a halide, of acid, is reacted in the presence of an acid catalyst general formula II: in which X and R retain the abovementioned meanings with an aldehyde of general formula III: in which R 2 retains the abovementioned meanings.
  • the subject of the invention is in particular a process as defined above, for the preparation of the compounds of general formula I, as defined above, process characterized in that an acid halide of general formula is used at the start II A : in which R and X keep the above-mentioned meanings.
  • the acid catalyst in the presence of which the condensation of the acid halide II and of the aldehyde III is carried out, is preferably either a Lewis acid such as zinc chloride, aluminum chloride or ferric chloride, either a protonic acid such as paratoluene sulfonic acid or oleum.
  • the condensation of the acid halide (II) and the aldehyde (III) is conveniently carried out by simple mixing of the reactants and the acid catalyst, without addition of solvent.
  • This condensation can also be carried out in the presence of an organic solvent.
  • the subject of the invention is also a process for preparing the compounds of general formula I in which X represents a fluorine atom and in which R 2 represents either a residue: in which A represents a group: a group or a group: characterized in that a quaternary ammonium fluoride attached to a resin is reacted with a chloride (Z,) or of formula either of formula: either of formula: either of formula: subject, in the presence of azoisobutyronitrile, the corresponding resulting fluoride (Z 2 ) to the action of N-bromosuccinimide to obtain a mixed brominated and fluorinated derivative (Z 3 ) or of formula: either formula either of formula: either of formula: then reacts this compound with an alkaline salt of general formula IV: wherein R retains the above meanings and M represents an ion derived from an alkali metal.
  • a resin of the Amberlite A type 26 is advantageously used, sold by the company ROHM and HAAS, which is washed by percolation with a solution. aqueous soda, then washed with water until neutral. The wet resin is then stirred in an aqueous solution of hydrofluoric acid, washed with water and then dried by washing with organic solvents.
  • the fluorination of the chloride (Z,) by the resin thus prepared is advantageously carried out in an organic solvent such as toluene.
  • the condensation of the mixed brominated and fluorinated derivative (Z3) and of the sodium salt of acid IV is advantageously carried out in an organic solvent such as dimethylformamide.
  • the compounds of formula I A as defined above, have been found to be endowed with an interesting insecticidal activity and can be used as insecticides in the domestic and agricultural fields.
  • the compounds of formula I A can be used to prepare, according to the usual methods, insecticidal compositions. These compositions preferably contain from 0.05 to 10% by weight of active material and, in general, a vehicle and / or a nonionic surfactant.
  • the compounds of formula I A are useful intermediates in the synthesis of esters having remarkable pesticidal properties, in particular insecticides.
  • a subject of the invention is therefore also the application of the compounds of formula I A , as defined above, to the preparation, in all their stereoisomeric forms or in the form of a mixture of stereoisomers, of the compounds of formula I B : in which R 1 and R 2 retain the same meanings as in formula I A , application characterized in that a compound generating CN- ions is reacted with a compound of general formula I A : in which X, R 1 and R 2 retain the abovementioned meanings, the resulting compounds I B existing in the stereoisomeric forms corresponding to the stereoisomeric forms of the compounds I A used.
  • the subject of the invention is in particular an application of the compounds of formula I, as defined above, to the preparation of the products of formula I C : in which R and R 2 are defined as above, application characterized in that a compound generating CN- ions is reacted with a compound of general formula I.
  • Condensation of the compound of general formula I A or 1 with the ion generating agent CN- is conveniently carried out in an anhydrous organic solvent, chosen from the group consisting of acetonitrile and dimethylformamide.
  • the agent generating CN- ions which is made to act on the compound of formula I A or I is preferably an alkaline cyanide, such as sodium or potassium cyanide.
  • cyanidation agent tetraethyl ammonium cyanide, 1-methyl 1-ethyl ethanonitrile, cuprous cyanide.
  • a more particular subject of the invention is an application to the preparation, according to the above method, of 1 R, cis 2,2-dimethyl 3- (2 ', 2'-dibromovinyl) cyclopropane-1-carboxylate of RS a- cyano-3-phenoxy benzyl, characterized in that the starting compound used is 1 R, cis 2,2-dimethyl 3- (2 ', 2'-dibromovinyl) cyclopropane-1-carboxylate of RS a-chloro 3-phenoxy benzyl, an application to the preparation, according to the above method, of 1 R, cis 2,2-dimethyl 3- (2 ', 2'-dibromovinyl) cyclopropane-1-carboxylate of RS a-cyano 3-phenoxy benzyl, characterized in that the starting compound used is 1R, cis 2,2-dimethyl 3- (2 ', 2'-dibromovinyl) cyclopropane.
  • the process for preparing the compounds of formula I A and the application of these to the preparation of the compounds of formula I B constitute a new process for economical access to the compounds I B. It has the advantage of using reagents which are easily accessible and of producing compounds I B in high yields.
  • this process avoids the use of a-cyano 3-phenoxy benzyl alcohol, a fragile and delicate compound to handle.
  • the compounds of formula II used at the start of the process are known compounds.
  • the acid chlorides of general formula: are described in French patent application 2 364 884 which also includes the preparation of the corresponding acids.
  • the other acid halides are obtained according to conventional methods from the acids described in French patent application 2,364,884.
  • the chloride of 1R acid, cis 2,2-dimethyl 3- (2 ', 2'-dibromovinyl) cyclopropane-1-carboxylic can be obtained in a manner analogous to that described in Examples 16 and 17 of French patent 2,185 .612.
  • This compound can be obtained by the action of 1R acid fluoride, cis 2,2-dimethyl 3- (2 ', 2'-dibromovinyl) cyclopropane 1-carboxylic acid with metaphenoxybenzoic aldehyde in the presence of zinc chloride.
  • the mixture is heated at 100 ° C., for 20 hours, with stirring, a mixture of 10.5 g of methaphenoxy benzyl chloride, 150 cm 3 of toluene and 40 g of resin obtained in paragraph a).
  • the resin is removed by filtration, washed with methylene chloride, the solvents are removed by distillation under reduced pressure, the residue is rectified and 5.8 g of metaphenoxy benzyl fluoride (bp 93 ° C under 0.05 mm of mercury) are obtained. ).
  • the NMR spectrum shows the absence of aldehyde proton.
  • Example 13 Analogously to that of Example 13, starting from the ⁇ -brominated derivative obtained in Example 5, the 1 R, cis 2,2-dimethyl 3- (2 ', 2'-dibromovinyl) cyclopropane 1 is obtained -carboxylate of RS a-cyano 3-phenoxy benzyl.
  • a series of tests without synergistic agent and a series of tests with synergism are carried out with piperonyl butoxide in the proportion 10 parts of piperonyl butoxide for 1 part of product to be tested.
  • the mortality check is carried out twenty-four hours after treatment.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Agricultural Chemicals And Associated Chemicals (AREA)
  • Furan Compounds (AREA)
  • Indole Compounds (AREA)

Description

La présente invention a pour objet, sous toutes leurs formes stéréoisomères ou sous forme de mélange de stéréoisomères, les composés de formule générale IA:

Figure imgb0001
dans laquelle:

  • - X représente un atome de fluor, de chlore ou de brome,
  • - R1 représente:
    • soit un groupement R1'
      Figure imgb0002
      dans lequel
    • ou bien Y1 et Y2, sont identiques et représentent un radical méthyle,
    • ou bien Y1 représente un atome d'hydrogène et Y2 représente un groupement Y2':
      Figure imgb0003
      ou bien Y1 représente un atome d'hydrogène et Y2 représente un groupement:
      Figure imgb0004
      Y3 et Y4, identiques ou différents, représentant un atome de fluor, de chlore ou de brome, ou bien Y et Y4, identiques ou différents, représentant un radical méthyle ou un atome d'hydrogène, le groupement R1' correspondant, dans le cas où Y2 représente un groupement:
      Figure imgb0005
      à un reste d'acide de structure cis ou trans, racémique ou optiquement actif, ou à un mélange de restes d'acide de structure cis et d'acide de structure trans,
    • soit un groupement (R1"):
      Figure imgb0006
      dans lequel Z représente un atome d'hydrogène, un atome de fluor, de chlore ou de brome, un radical alcoyle, linéaire ou ramifié, comportant de 1 à 4 atomes de carbone, un radical alcoyloxy, linéaire ou ramifié, comportant de 1 à 4 atomes de carbone, le groupement (R1") correspondant à un reste d'acide racémique ou optiquement actif,
  • R2 représente, dans le cas où Y2 est différent de Y2':
    • ou bien un reste choisi parmi les groupements suivants:
      Figure imgb0007
      Figure imgb0008
      ou bien le reste
      Figure imgb0009
      dans lequel A représente soit un groupement:
      Figure imgb0010
      soit un groupement
      Figure imgb0011
      soit un groupement:
      Figure imgb0012
      soit un groupement
      Figure imgb0013
      soit un groupement
      Figure imgb0014
      ou R2 représente, dans le cas où Y2 représente un groupe Y2', le reste
      Figure imgb0015
      dans lequel A représente un groupement
      Figure imgb0016
  • L'invention a notamment pour objet, sous toutes leurs formes stéréoisomères, les composés de formule générale I:
    Figure imgb0017
    dans laquelle R2 et X sont définis comme précédemment, et R représente soit un groupement R':
    Figure imgb0018
    dans lequel:
    • ou bien Y1 et Y2, sont identiques et représentent un radical méthyle,
    • ou bien Y1 représente un atome d'hydrogène et Y2 représente un groupement:
      Figure imgb0019
      Y3 et Y4, identiques ou différents, représentant un atome de fluor, de chlore ou de brome, ou bien Y3 et Y4, identiques ou différents, représentant un radical méthyle ou un atome d'hydrogène, le groupement R1' correspondant, dans le cas où Y2 représente un groupement:
      Figure imgb0020
      à un reste d'acide de structure cis ou trans, racémique ou optiquement actif, ou à un mélange de restes d'acide de structure cis et d'acide de structure trans.
      • - soit un groupement R," tel que défini précédemment.
    • Les composés (IA) existent sous de nombreuses formés stéréoisomères.
  • Lorsque, dans le groupement R1', Y, représente un atome d'hydrogène et Y2 représente un groupement:
    Figure imgb0021
    le groupement R1 possède deux carbones asymétriques en positions 1 et 3 du cycle cyclopropanique. Les acides cyclopropane carboxyliques correspondants peuvent être alors de structure cis ou de structure trans, racémiques ou optiquement actifs, ou peuvent être des mélanges d'acides de structure cis et d'acides de structure trans.
The subject of the present invention is, in all their stereoisomeric forms or in the form of a mixture of stereoisomers, the compounds of general formula I A :
Figure imgb0001
 in which:
  • - X represents a fluorine, chlorine or bromine atom,
  • - R 1 represents:
    • or a group R 1 '
      Figure imgb0002
       in which
    • or else Y 1 and Y 2 , are identical and represent a methyl radical,
    • or else Y 1 represents a hydrogen atom and Y 2 represents a group Y 2 ':
      Figure imgb0003
       or else Y 1 represents a hydrogen atom and Y 2 represents a group:
      Figure imgb0004
       Y 3 and Y 4 , identical or different, representing a fluorine, chlorine or bromine atom, or else Y and Y 4 , identical or different, representing a methyl radical or a hydrogen atom, the group R 1 'corresponding , in the case where Y 2 represents a group:
      Figure imgb0005
       to a residue of acid of cis or trans structure, racemic or optically active, or to a mixture of residues of acid of cis structure and of acid of trans structure,
    • or a group (R 1 "):
      Figure imgb0006
       in which Z represents a hydrogen atom, a fluorine, chlorine or bromine atom, an alkyl radical, linear or branched, comprising from 1 to 4 carbon atoms, an alkyloxy radical, linear or branched, comprising from 1 to 4 carbon atoms, the group (R 1 ") corresponding to a residue of racemic or optically active acid,
  • R 2 represents, in the case where Y 2 is different from Y 2 ':
    • or a remainder chosen from the following groups:
      Figure imgb0007
      Figure imgb0008
       or the rest
      Figure imgb0009
       in which A represents either a group:
      Figure imgb0010
       either a group
      Figure imgb0011
       either a group:
      Figure imgb0012
       either a group
      Figure imgb0013
       either a group
      Figure imgb0014
       or R 2 represents, in the case where Y 2 represents a group Y 2 ', the remainder
      Figure imgb0015
       in which A represents a group
      Figure imgb0016
  • The subject of the invention is in particular, in all their stereoisomeric forms, the compounds of general formula I:
    Figure imgb0017
     in which R 2 and X are defined as above, and R represents either a group R ':
    Figure imgb0018
     in which:
    • or else Y 1 and Y 2 , are identical and represent a methyl radical,
    • or else Y 1 represents a hydrogen atom and Y 2 represents a group:
      Figure imgb0019
       Y 3 and Y 4 , identical or different, representing a fluorine, chlorine or bromine atom, or else Y 3 and Y 4 , identical or different, representing a methyl radical or a hydrogen atom, the group R 1 ' corresponding, in the case where Y 2 represents a group:
      Figure imgb0020
       to a residue of acid of cis or trans structure, racemic or optically active, or to a mixture of residues of acid of cis structure and of acid of trans structure.
      • - or a group R, "as defined above.
    • Compounds (I A ) exist in many stereoisomeric forms.
  • When, in the group R 1 ′, Y represents a hydrogen atom and Y 2 represents a group:
    Figure imgb0021
     the group R 1 has two asymmetric carbons in positions 1 and 3 of the cyclopropane ring. The corresponding cyclopropane carboxylic acids may then be of cis structure or of trans structure, racemic or optically active, or may be mixtures of acids of cis structure and acids of trans structure.

Dans le cas où Y3 est différent de Y4 il existe, de plus, une isomérie (E) et (Z) au niveau de la double liaison.In the case where Y 3 is different from Y 4 there is, moreover, an isomerism (E) and (Z) at the level of the double bond.

Le groupement R1" dérive d'acides 2-aryl 2-isopropyl acétiques substitués dont le carbone en position 2 est un carbone asymétrique, ce qui entraïne dans ce groupement l'existence de deux formes énantiomères et d'un racémique.The group R 1 "is derived from substituted 2-aryl 2-isopropyl acetic acids whose carbon in position 2 is an asymmetric carbon, which brings about in this group the existence of two enantiomeric forms and of a racemic.

De plus, dans les composés de formule IA; le carbone porteur du substituant X est un carbone asymétrique.In addition, in the compounds of formula I A ; the carbon carrying the substituent X is an asymmetric carbon.

On peut considérer comme vraisemblable que, d'après le procédé d'obtention des composés de formule IA, dans le cas où le groupement R1 comporte un ou plusieurs carbones asymétriques de configuration absolue bien définie, il y ait une induction asymétrique au niveau du carbone porteur de X. Mais l'induction ainsi obtenue n'est, en général, pas totale et le centre chiral (porteur de X) n'est, en général, ni entièrement de structure (R), ni entièrement de structure (S). Il en résulte que le produit IA obtenu, dans ce cas, est un mélange de deux diastéréoisomères que l'on peut séparer. Ces diastéréoisomères seront appelés par la suite, isomère A et isomère B.It can be considered likely that, according to the process for obtaining the compounds of formula I A , in the case where the group R 1 comprises one or more asymmetric carbons of well defined absolute configuration, there is an asymmetric induction at the level carbon carrying X. But the induction thus obtained is, in general, not total and the chiral center (carrier of X) is, in general, neither entirely of structure (R), nor entirely of structure ( S). It follows that the product I A obtained, in this case, is a mixture of two diastereoisomers which can be separated. These diastereoisomers will be called hereinafter, isomer A and isomer B.

Par convention, l'isomère A est celui des deux qui est le plus mobile en chromatographie sur couche mince. D'après certaines considérations théoriques mais sans vouloir être lié par l'exactitude de l'attribution des chiralités que l'on en déduit, il est plausible d'attribuer à l'isomère A, la configuration absolue (S) pour le carbone porteur du substituant X.By convention, the A isomer is the one of the two which is the most mobile in thin layer chromatography. According to certain theoretical considerations but without wishing to be bound by the accuracy of the attribution of the chiralities which we deduce therefrom, it is plausible to attribute to the isomer A, the absolute configuration (S) for the carbon carrier of the substituent X.

L'atome de carbone asymétrique de la chaîne latérale éthylique des composés de formule IA dans laquelle R1 représente un groupement R1' dans lequel Y1 représente un atome d'hydrogène et Y2 représente un groupement

Figure imgb0022
entraîne, pour sa part, l'existence de deux diastéréoisomères que l'on peut séparer, par exemple, par chromatographie.The asymmetric carbon atom of the ethyl side chain of the compounds of formula I A in which R 1 represents a group R 1 'in which Y 1 represents a hydrogen atom and Y 2 represents a group
Figure imgb0022
 for its part, results in the existence of two diastereoisomers which can be separated, for example, by chromatography.

Les composés de formule IA de l'invention, englobent pour une définition donnée des substituants X, R1 et R2, tous les composés provenant de la combinaison d'un isomèré; optiquement actif (ou racémique), résultant de l'existence du ou des carbones asymétriques de la partie acide R1 de la molécule avec un isomère optiquement actif (ou racémique) correspondant à la copule alcoolique:

Figure imgb0023
The compounds of formula I A of the invention include, for a given definition of the substituents X, R 1 and R 2 , all the compounds originating from the combination of an isomer; optically active (or racemic), resulting from the existence of the asymmetric carbon (s) of the acid part R 1 of the molecule with an optically active (or racemic) isomer corresponding to the alcoholic copula:
Figure imgb0023

L'invention a notamment pour objet les composés de formule 1 comportant un groupement (R') dans lequel Y, représente un atome d'hydrogène et Y2 représente un groupement:

Figure imgb0024
The invention particularly relates to the compounds of formula 1 comprising a group (R ') in which Y represents a hydrogen atom and Y 2 represents a group:
Figure imgb0024

Parmi les composés, objet de l'invention, on citera plus particulièrement ceux dans lesquels R2 représente un groupement

Figure imgb0025
A ayant pour valeur
Figure imgb0026
ceux dans lesquels X représente un atome de fluor; ceux dans lesquels R2 représente un groupement
Figure imgb0027
A ayant pour valeur
Figure imgb0028
et dans lesquels X représente un atome de fluor ou de brome ainsi que ceux dans lesquels X représente un atome de chlore.Among the compounds which are the subject of the invention, mention will be made more particularly of those in which R 2 represents a group
Figure imgb0025
 A having for value
Figure imgb0026
 those in which X represents a fluorine atom; those in which R 2 represents a group
Figure imgb0027
 A having for value
Figure imgb0028
 and in which X represents a fluorine or bromine atom as well as those in which X represents a chlorine atom.

Parmi les composés de formule générale IA, les produits décrits dans les exemples et notamment:

  • - le 1 R, cis 2,2-diméthyl 3-(2',2'-dibromovinyl)cyclopropane-1-carboxylate de (RS) α-chloro 3- phénoxy benzyle,
  • - le 1 R, cis 2,2-diméthyl 3-(2',2'-dibromovinyl)cyclopropane-1-carboxylate de (RS) α-fluoro 3- phénoxy benzyle,
  • - le 1 R, cis 2,2-diméthyl 3-(2',2'-dichlorovinyl)cyclopropane-1-carboxylate de (RS) α-chloro 3- phénoxy benzyle,
  • - le 2-(parachlorophényl) 2-isopropyl acétate de (RS) a-chloro 3-phénoxy benzyle et
  • - le 1 R, trans 2,2-diméthyl 3-(1',2'-dibromo 2' 2'-dichloroéthyl) cyclopropane 1-carboxylate de (R,S) a-chloro 3-phénoxybenzyle sont particulièrement intéressants.
Among the compounds of general formula I A , the products described in the examples and in particular:
  • - 1 R, cis 2,2-dimethyl 3- (2 ', 2'-dibromovinyl) cyclopropane-1-carboxylate of (RS) α-chloro 3- phenoxy benzyl,
  • - 1 R, cis 2,2-dimethyl 3- (2 ', 2'-dibromovinyl) cyclopropane-1-carboxylate from (RS) α-fluoro 3- phenoxy benzyl,
  • - 1 R, cis 2,2-dimethyl 3- (2 ', 2'-dichlorovinyl) cyclopropane-1-carboxylate of (RS) α-chloro 3- phenoxy benzyl,
  • - 2- (parachlorophenyl) 2-isopropyl acetate of (RS) a-chloro 3-phenoxy benzyl and
  • - 1 R, trans 2,2-dimethyl 3- (1 ', 2'-dibromo 2'2'-dichloroethyl) cyclopropane 1-carboxylate of (R, S) a-chloro 3-phenoxybenzyl are particularly interesting.

L'invention a également pour objet un procédé de préparation des composés de formule générale IA, telle que définie précédemment, procédé caractérisé en ce que l'on fait réagir, en présence d'un catalyseur acide, un halogénure, d'acide de formule générale II:

Figure imgb0029
dans laquelle X et R, conservent les significations précitées avec un aldéhyde de formule générale III:
Figure imgb0030
dans laquelle R2 conserve les significations précitées.The subject of the invention is also a process for the preparation of the compounds of general formula I A , as defined above, a process characterized in that a halide, of acid, is reacted in the presence of an acid catalyst general formula II:
Figure imgb0029
 in which X and R retain the abovementioned meanings with an aldehyde of general formula III:
Figure imgb0030
 in which R 2 retains the abovementioned meanings.

L'invention a notamment pour objet un procédé tel que défini ci-dessus, pour la préparation des composés de formule générale I, telle que définie précédemment, procédé caractérisé en ce que l'on utilise au départ un halogénure d'acide de formule générale IIA:

Figure imgb0031
dans laquelle R et X conservent les significations précitées.The subject of the invention is in particular a process as defined above, for the preparation of the compounds of general formula I, as defined above, process characterized in that an acid halide of general formula is used at the start II A :
Figure imgb0031
 in which R and X keep the above-mentioned meanings.

La préparation des chlorures ou des bromures d'acide de formule (II) ou (IIA) est effectuée par les méthodes classiques.The preparation of chlorides or acid bromides of formula (II) or (II A ) is carried out by conventional methods.

La préparation des fluorures d'acide de formule II est avantageusement effectuée selon la méthode décrite par MUKAIYAMA, Chem. Letters p. 303-306 (1976).The preparation of the acid fluorides of formula II is advantageously carried out according to the method described by MUKAIYAMA, Chem. Letters p. 303-306 (1976).

Le catalyseur acide, en présence duquel est effectué la condensation de l'halogénure d'acide II et de l'aldéhyde III est, de préférence,, soit un acide de Lewis tel que le chlorure de zinc, le chlorure d'aluminium ou le chlorure ferrique, soit un acide protonique tel que l'acide paratoluène sulfonique ou l'oléum.The acid catalyst, in the presence of which the condensation of the acid halide II and of the aldehyde III is carried out, is preferably either a Lewis acid such as zinc chloride, aluminum chloride or ferric chloride, either a protonic acid such as paratoluene sulfonic acid or oleum.

La condensation de l'halogénure d'acide (II) et de l'aldéhyde (III) est effectuée commodément par simple mélange des réactifs et du catalyseur acide, sans addition de solvant.The condensation of the acid halide (II) and the aldehyde (III) is conveniently carried out by simple mixing of the reactants and the acid catalyst, without addition of solvent.

Cette condensation peut aussi être effectuée en présence d'un solvant organique.This condensation can also be carried out in the presence of an organic solvent.

L'invention a aussi pour objet un procédé de préparation des composés de formule générale I dans lesquels X représente un atome de fluor et dans lesquels R2 représente soit un reste:

Figure imgb0032
dans lequel A représente un groupement:
Figure imgb0033
un groupement
Figure imgb0034
ou un groupement:
Figure imgb0035
caractérisé en ce que l'on fait réagir un fluorure d'ammonium quaternaire fixé sur une résine avec un chlorure (Z,) soit de formule
Figure imgb0036
soit de formule:
Figure imgb0037
soit de formule:
Figure imgb0038
soit de formule:
Figure imgb0039
soumet, en présence d'azoisobutyronitrile, le fluorure (Z2) résultant correspondant, à l'action du N-bromosuccinimide pour obtenir un dérivé mixte bromé et fluoré (Z3) soit de formule:
Figure imgb0040
soit de formule
Figure imgb0041
soit de formule:
Figure imgb0042
soit de formule:
Figure imgb0043
puis fait réagir ce composé avec un sel alcalin de formule générale IV:
Figure imgb0044
dans laquelle R conserve les significations précitées et M représente un ion dérivant d'un métal alcalin.The subject of the invention is also a process for preparing the compounds of general formula I in which X represents a fluorine atom and in which R 2 represents either a residue:
Figure imgb0032
 in which A represents a group:
Figure imgb0033
 a group
Figure imgb0034
 or a group:
Figure imgb0035
 characterized in that a quaternary ammonium fluoride attached to a resin is reacted with a chloride (Z,) or of formula
Figure imgb0036
 either of formula:
Figure imgb0037
 either of formula:
Figure imgb0038
 either of formula:
Figure imgb0039
 subject, in the presence of azoisobutyronitrile, the corresponding resulting fluoride (Z 2 ) to the action of N-bromosuccinimide to obtain a mixed brominated and fluorinated derivative (Z 3 ) or of formula:
Figure imgb0040
 either formula
Figure imgb0041
 either of formula:
Figure imgb0042
 either of formula:
Figure imgb0043
 then reacts this compound with an alkaline salt of general formula IV:
Figure imgb0044
 wherein R retains the above meanings and M represents an ion derived from an alkali metal.

Pour la préparation du fluorure (Z2), on utilise avantageusement une résine du type Amberlite A. 26, commercialisée par la firme ROHM et HAAS, que l'on lave par percolation avec une solution aqueuse de soude, puis que l'on lave a l'eau jusqu'à neutralité. Le résine humide est ensuite agitée dans une solution aqueuse d'acide fluorhydrique, lavée à l'eau puis séchée par lavage avec des solvants organiques.For the preparation of fluoride (Z 2 ), a resin of the Amberlite A type 26 is advantageously used, sold by the company ROHM and HAAS, which is washed by percolation with a solution. aqueous soda, then washed with water until neutral. The wet resin is then stirred in an aqueous solution of hydrofluoric acid, washed with water and then dried by washing with organic solvents.

La fluoration du chlorure (Z,) par la résine ainsi préparée est effectuée avantageusement au sein d'un solvant organique tel que le toluène.The fluorination of the chloride (Z,) by the resin thus prepared is advantageously carried out in an organic solvent such as toluene.

L'obtention du dérivé mixte bromé et fluoré (Z3) par condensation du fluorure Z2 et du N-bromosuccinimide, en présence d'azoisobutyronitrile est commodément effectuée au sein du tétrachlorure de carbone en opérant au reflux.Obtaining the mixed brominated and fluorinated derivative (Z 3 ) by condensation of the fluoride Z 2 and of N-bromosuccinimide, in the presence of azoisobutyronitrile is conveniently carried out in carbon tetrachloride by operating at reflux.

La condensation du dérivé mixte bromé et fluoré (Z3) et du sel de sodium de l'acide IV est avantageusement effectuée au sein d'un solvant organique tel que le diméthylformamide.The condensation of the mixed brominated and fluorinated derivative (Z3) and of the sodium salt of acid IV is advantageously carried out in an organic solvent such as dimethylformamide.

Les composés de formule IA, telle que définie précédemment, se sont avérés être doués d'une activité insecticide intéressante et peuvent être utilisés comme insecticides dans les domaines domestique et agricole.The compounds of formula I A , as defined above, have been found to be endowed with an interesting insecticidal activity and can be used as insecticides in the domestic and agricultural fields.

Cette activité insecticide s'est révélée particulièrement remarquable pour les composés de formule IA dans laquelle R2 représente un groupement

Figure imgb0045
A étant un radical phénoxy.This insecticidal activity has proved particularly remarkable for the compounds of formula I A in which R 2 represents a group
Figure imgb0045
 A being a phenoxy radical.

Les composés de formule IA peuvent être utilisés pour préparer, selon les méthodes usuelles, des compositions insecticides. Ces compositions contiennent, de préférence, de 0,05 à 10% en poids de matière active et, en générale, un véhicule et/ou un agent tensio actif non ionique.The compounds of formula I A can be used to prepare, according to the usual methods, insecticidal compositions. These compositions preferably contain from 0.05 to 10% by weight of active material and, in general, a vehicle and / or a nonionic surfactant.

Les composés de formule IA,telle que définie précédemment, sont des intermédiaires utiles dans la synthèse d'esters possédant de remarquables propriétés pesticides, notamment insecticides.The compounds of formula I A , as defined above, are useful intermediates in the synthesis of esters having remarkable pesticidal properties, in particular insecticides.

L'invention a ainsi également pour objet l'application des composés de formule IA, telle que définie précédemment, à la préparation, sous toutes leurs formes stéréoisomères ou sous forme de mélange de stéréoisomères, des composés de formule IB:

Figure imgb0046
dans laquelle R1 et R2 conservent les mêmes significations que dans la formule IA, application caractérisée en ce que l'on fait réagir un composé générateur d'ions CN- sur un composé de formule générale IA:
Figure imgb0047
dans laquelle X, R1 et R2 conservent les significations précitées, les composés IB résultants existant sous les formes stéréoisomères correspondant aux formes stéréoisomères des composés IA utilisés.A subject of the invention is therefore also the application of the compounds of formula I A , as defined above, to the preparation, in all their stereoisomeric forms or in the form of a mixture of stereoisomers, of the compounds of formula I B :
Figure imgb0046
 in which R 1 and R 2 retain the same meanings as in formula I A , application characterized in that a compound generating CN- ions is reacted with a compound of general formula I A :
Figure imgb0047
 in which X, R 1 and R 2 retain the abovementioned meanings, the resulting compounds I B existing in the stereoisomeric forms corresponding to the stereoisomeric forms of the compounds I A used.

L'invention a notamment pour objet une application des composés de formule I, telle que définie ci-dessus, à la préparation des produits de formule IC:

Figure imgb0048
dans laquelle R et R2 sont définis comme précédemment, application caractérisée en ce que l'on fait réagir un composé générateur d'ions CN- sur un composé de formule générale I.The subject of the invention is in particular an application of the compounds of formula I, as defined above, to the preparation of the products of formula I C :
Figure imgb0048
 in which R and R 2 are defined as above, application characterized in that a compound generating CN- ions is reacted with a compound of general formula I.

Le procédé est particulièrement avantageux lorsque, dans la formule IA ou I, X représente un atome de fluor ou de chlore.The process is particularly advantageous when, in formula I A or I, X represents a fluorine or chlorine atom.

La condensation du composé de formule générale IA ou 1 avec l'agent générateur d'ions CN- est effectuée commodément au sein d'un solvant organique anhydre, choisi dans le groupe constitué par l'acétonitrile et le diméthylformamide.Condensation of the compound of general formula I A or 1 with the ion generating agent CN- is conveniently carried out in an anhydrous organic solvent, chosen from the group consisting of acetonitrile and dimethylformamide.

L'agent générateur d'ions CN- que l'on fait agir sur le composé de formule IA ou I est, de préférence, un cyanure alcalin, tel que le cyanure de sodium ou de potassium.The agent generating CN- ions which is made to act on the compound of formula I A or I is preferably an alkaline cyanide, such as sodium or potassium cyanide.

On peut également utiliser, avantageusement, comme agent de cyanuration, le cyanure de tétraéthyl ammonium, le 1-méthyl 1-éthyl éthanonitrile, le cyanure cuivreux.It is also advantageous to use, as cyanidation agent, tetraethyl ammonium cyanide, 1-methyl 1-ethyl ethanonitrile, cuprous cyanide.

Les produits de formule, IB ou IC obtenus sous forme de mélanges d'isomères, notamment au niveau du carbone porteur du groupement -CN, peuvent être séparés en leurs différents constituants par des méthodes connues.The products of formula, I B or I C obtained in the form of mixtures of isomers, in particular at the level of the carbon carrying the group -CN, can be separated into their different constituents by known methods.

L'invention a plus particulièrement pour objet, une application à la préparation, selon la méthode précitée, du 1 R, cis 2,2-diméthyl 3-(2',2'-dibromovinyl) cyclopropane-1-carboxylate de RS a-cyano 3- phénoxy benzyle, caractérisée en ce que le composé de départ utilisé est le 1 R, cis 2,2-diméthyl 3-(2',2'-dibromovinyl) cyclopropane-1-carboxylate de RS a-chloro 3-phénoxy benzyle, une application à la préparation, selon la méthode précitée, du 1 R, cis 2,2-diméthyl 3-(2',2'-dibromovinyl) cyclopropane-1-carboxylate de RS a-cyano 3-phénoxy benzyle, caractérisée en ce que le composé de départ utilisé est le 1R, cis 2,2-diméthyl 3-(2',2'-dibromovinyl) cyclopropane.1-carboxylate de RS α-fluoro 3-phénoxy benzyle, une application à la préparation, selon la méthode précitée, du 1 R, cis 2,2-diméthyl 3-(2',2'-dichlorovinyl) cyclopropane 1-carboxylate de RS a-cyano 3-phénoxy benzyle, caractérisée en ce que le composé de départ utilisé est le 1 R, cis 2,2-diméthyl 3-(2',2'-dichlorovinyl) cyclopropane 1-carboxylate de RS α-chloro 3-phénoxy benzyle, une application à la préparation, selon la méthode précitée, du 2- parachlorophényl 2-isopropyl acétate de RS a-cyano 3-phénoxy benzyle, caractérisé en ce que le composé de départ utilisé est le 2-parachlorophényl 2-isopropyl acétate de RS α-chloro 3-phénoxy benzyle, une application à la préparation, selon la méthode précitée, du 1 R, trans 2,2-diméthyl 3-(1',2'-dibromo 2,2'-dichloroéthyl) cyclopropane 1-carboxylate de (R,S) a-cyano 3-phénoxy benzyle, caractérisée en ce que le composé de départ utilisé est le 1R, trans 2,2-diméthyl 3-(1',2'-dibromo 2',2'-dichloroéthyl) cyclopropane 1-carboxylate de (R,S) a-chloro ou a-fluoro 3-phénoxy benzyle.A more particular subject of the invention is an application to the preparation, according to the above method, of 1 R, cis 2,2-dimethyl 3- (2 ', 2'-dibromovinyl) cyclopropane-1-carboxylate of RS a- cyano-3-phenoxy benzyl, characterized in that the starting compound used is 1 R, cis 2,2-dimethyl 3- (2 ', 2'-dibromovinyl) cyclopropane-1-carboxylate of RS a-chloro 3-phenoxy benzyl, an application to the preparation, according to the above method, of 1 R, cis 2,2-dimethyl 3- (2 ', 2'-dibromovinyl) cyclopropane-1-carboxylate of RS a-cyano 3-phenoxy benzyl, characterized in that the starting compound used is 1R, cis 2,2-dimethyl 3- (2 ', 2'-dibromovinyl) cyclopropane.1-RS carboxylate α-fluoro 3-phenoxy benzyl, an application to the preparation, according to the aforementioned method, 1 R, cis 2,2-dimethyl 3- (2 ', 2'-dichlorovinyl) cyclopropane 1-carboxylate of RS a-cyano 3-phenoxy benzyl, characterized in that the starting compound used is 1 R, cis 2,2-dimethyl 3- (2 ', 2'-dichlorovinyl) cycloprop ane 1-carboxylate of RS α-chloro 3-phenoxy benzyl, an application to the preparation, according to the above method, of 2-parachlorophenyl 2-isopropyl acetate of RS a-cyano 3-phenoxy benzyl, characterized in that the compound of starting material used is 2-parachlorophenyl 2-isopropyl acetate of RS α-chloro 3-phenoxy benzyl, an application to the preparation, according to the above method, of 1 R, trans 2,2-dimethyl 3- (1 ', 2' -dibromo 2,2'-dichloroethyl) cyclopropane 1-carboxylate of (R, S) a-cyano 3-phenoxy benzyl, characterized in that the starting compound used is 1R, trans 2,2-dimethyl 3- (1 ', 2'-dibromo 2', 2'-dichloroethyl) cyclopropane 1-carboxylate of (R, S) a-chloro or a-fluoro 3-phenoxy benzyl.

De nombreux composés de formule IB sont bien connus pour leurs propriétés insecticides particulièrement intenses (voir notamment le brevet français 2 185 612 et la demande française publiée sous le n° 2 364 884).Many compounds of formula I B are well known for their particularly intense insecticidal properties (see in particular French patent 2,185,612 and French application published under No. 2,364,884).

On peut citer à ce sujet, le 1 R, cis 2,2-diméthyl 3-(2'2'-dibromovinyl) cyclopropane 1-carboxylate de RS α-cyano 3-phénoxy benzyle, le 1 R, cis 2,2-diméthyl 3-(2',2'-dichlorovinyl) cyclopropane 1-carboxylate de RS α-cyano 3-phénoxy benzyle ou le 1 R, trans 2,2-diméthyl 3-(1',2'-dibromo 2',2'-dichloroéthyl) cyclopropane 1-carboxylate de R,S α-cyano 3-phénoxy benzyle.Mention may be made on this subject, 1 R, cis 2,2-dimethyl 3- (2'2'-dibromovinyl) cyclopropane 1-carboxylate of RS α-cyano 3-phenoxy benzyl, 1 R, cis 2,2- dimethyl 3- (2 ', 2'-dichlorovinyl) cyclopropane 1-carboxylate of RS α-cyano 3-phenoxy benzyl or the 1 R, trans 2,2-dimethyl 3- (1', 2'-dibromo 2 ', 2 '-dichloroethyl) cyclopropane 1-carboxylate of R, S α-cyano 3-phenoxy benzyl.

Le procédé de préparation des composés de formule IA et l'application de ceux-ci à la préparation des composés de formule IB, constituent un nouveau procédé d'accès économique aux composés IB. Il présente l'avantage d'utiliser des réactifs facilement accessibles et de conduire avec des rendements élevés aux composés IB.The process for preparing the compounds of formula I A and the application of these to the preparation of the compounds of formula I B , constitute a new process for economical access to the compounds I B. It has the advantage of using reagents which are easily accessible and of producing compounds I B in high yields.

De plus, ce procédé permet d'éviter l'utilisation de l'alcool a-cyano 3-phénoxy benzylique, composé fragile et délicat à manipuler.In addition, this process avoids the use of a-cyano 3-phenoxy benzyl alcohol, a fragile and delicate compound to handle.

Les composés, de formule Il utilisés au départ du procédé sont des composés connus. Parmi ceux-ci, les chlorures d'acide de formule générale:

Figure imgb0049
sont décrits dans la demande de brevet français 2 364 884 qui comporte également la préparation des acides correspondants. Les autres halogénures d'acide sont obtenus selon les méthodes classiques à partir des acides décrits dans la demande de brevet français 2 364 884.The compounds of formula II used at the start of the process are known compounds. Among these, the acid chlorides of general formula:
Figure imgb0049
 are described in French patent application 2 364 884 which also includes the preparation of the corresponding acids. The other acid halides are obtained according to conventional methods from the acids described in French patent application 2,364,884.

Les exemples suivants illustrent l'invention sans la limiter.The following examples illustrate the invention without limiting it.

Exemple 1Example 1 1R,cis 2,2-diméthyl 3-(2',2'-dibromovinyl)cycloprane-1-carboxylate de RS α-chloro 3-phénoxy benzyle1R, cis 2,2-dimethyl 3- (2 ', 2'-dibromovinyl) cycloprane-1-carboxylate of RS α-chloro 3-phenoxy benzyl

A un mélange de 6,4 g de chlorure de l'acide 1 R, cis 2,2-diméthyl 3-(2',2'-dibromovinyl)cyclopropane-1-carboxylique et de 4 g d'aldéhyde métaphénoxy benzoïque, on ajoute ensuite 10 mg de chlorure de zinc fondu (sous forme de poudre). On note un échauffement et un épaississement du milieu. On laisse encore une heure en contact à 20°C et dans des conditions rigoureusement anhydres. On obtient le 1R,cis 2,2-diméthyl 3-(2',2'-dibromovinyl)cyctopropane-1-carboxylate de RS a-chloro-3-phénoxy benzyle brut.To a mixture of 6.4 g of 1 R acid chloride, cis 2,2-dimethyl 3- (2 ', 2'-dibromovinyl) cyclopropane-1-carboxylic acid and 4 g of metaphenoxy benzoic aldehyde, then add 10 mg of molten zinc chloride (in powder form). There is heating and thickening of the medium. Another hour is left in contact at 20 ° C and under strictly anhydrous conditions. 1R, cis 2,2-dimethyl 3- (2 ', 2'-dibromovinyl) cyctopropane-1-carboxylate of RS a-chloro-3-phenoxy benzyl is obtained.

Spectre Infra-Rouge (chloroforme)Infrared spectrum (chloroform)

Absorption à 1749 cm-1 caractéristique de C=O.Absorption at 1749 cm -1 characteristic of C = O.

Spectre de RMN (deutéro chloroforme)NMR spectrum (deutero chloroform)

  • Pics à 1,26-1,33 p.p.m. caractéristiques des hydrogènes des méthyles géminés,Peaks at 1.26-1.33 p.p.m. characteristics of the hydrogens of twin methyls,
  • pics à 1,85-2,10 p.p.m. caractéristiques des hydrogènes du cyclopropyle;peaks at 1.85-2.10 p.p.m. characteristics of the cyclopropyl hydrogens;
  • pics à 6,76-6,90 p.p.m. caractéristiques de l'hydrogène éthylénique;peaks at 6.76-6.90 p.p.m. characteristics of ethylenic hydrogen;
  • pics à 7,0 p.p.m. et 7,66 p.p.m. caractéristiques des hydrogènes du noyau aromatique et benzylique.peaks at 7.0 p.p.m. and 7.66 p.p.m. characteristics of the hydrogens of the aromatic and benzyl ring.

Le chlorure de l'acide 1R,cis 2,2-diméthyl 3-(2',2'-dibromovinyl)cyclopropane-1-carboxylique peut être obtenu d'une manière analogue à celle décrite aux exemples 16 et 17 du brevet français 2.185.612.The chloride of 1R acid, cis 2,2-dimethyl 3- (2 ', 2'-dibromovinyl) cyclopropane-1-carboxylic can be obtained in a manner analogous to that described in Examples 16 and 17 of French patent 2,185 .612.

Exemple 2Example 2 1R,cis 2.2-dimethyl 3-(2',2'-dibromovinyl)cyclopropane-1-carboxylate de RS α-chloro 3-phénoxy benzyle1R, cis 2.2-dimethyl 3- (2 ', 2'-dibromovinyl) cyclopropane-1-carboxylate de RS α-chloro 3-phenoxy benzyle

En opérant de manière analogue à celle de l'exemple 1 et en remplaçant les 10 mg de chlorure de zinc par 60 mg de chlorure ferrique et en agitant pendant quatre heures, on obtient le 1 R, cis 2,2-diméthyl 3-(2',2'-dibromovinyl)cyclopropane-1-carboxylate de RS α-chloro 3-phénoxy benzyle brut.By following a procedure analogous to that of Example 1 and replacing the 10 mg of zinc chloride with 60 mg of ferric chloride and stirring for four hours, 1 R, cis 2,2-dimethyl 3- ( 2 ', 2'-dibromovinyl) cyclopropane-1-carboxylate of RS α-chloro 3-phenoxy benzyl crude.

Exemple 3Example 3 1R,cis 2,2-diméthyl 3-(2',2'-dibromovinyl)cyclopropane-1-carboxylate de RS a-chloro 3-phénoxy benzyle.1R, cis 2,2-dimethyl 3- (2 ', 2'-dibromovinyl) cyclopropane-1-carboxylate of RS a-chloro 3-phenoxy benzyl.

En opérant de manière analogue à celle de l'exemple 1 en remplaçant les 10 mg de chlorure de zinc par 60 mg d'acide paratoluène sulfonique monohydraté et en agitant pendant vingt heures, on obtient le 1R,cis 2,2-diméthyl 3-(2',2'-dibromovinyl) cyclopropane-1-carboxylate de RS α-chloro 3- phénoxy benzyle brut.By following a procedure analogous to that of Example 1, replacing the 10 mg of zinc chloride with 60 mg of paratoluene sulfonic acid monohydrate and stirring for twenty hours, the 1R, cis 2,2-dimethyl 3- is obtained. (2 ', 2'-dibromovinyl) cyclopropane-1-carboxylate of RS α-chloro 3- phenoxy benzyl crude.

Exemple 4Example 4 1R,cis 2,2-diméthyl 3-(2',2'-dibromovinyl)cyclopropane-1-carboxylate de RS α-chloro 3-phénoxy benzyle.1R, cis 2,2-dimethyl 3- (2 ', 2'-dibromovinyl) cyclopropane-1-carboxylate of RS α-chloro 3-phenoxy benzyl.

En opérant de manière analogue à celle de l'exemple 1 et en remplaçant les 10 mg de chlorure de zinc par une goutte d'oléum à 65 pour cent, et en agitant pendant une heuré, on obtient le 1 R,cis 2,2-diméthyl 3-(2',2'-dibromovinyl)cyclopropane-1-carboxylate de RS α-chloro 3-phénoxy benzyle brut.By following a procedure analogous to that of Example 1 and replacing the 10 mg of zinc chloride with a drop of oleum at 65 percent, and stirring for one hour, the 1 R, cis 2.2 is obtained. -dimethyl 3- (2 ', 2'-dibromovinyl) cyclopropane-1-carboxylate of RS α-chloro 3-phenoxy benzyl crude.

Exemple 5Example 5 1R,cis 2,2-diméthyl 3-(2',2'-dibromovinyl)cyclopropane-1 carboxylate de RS α-bromo 3-phénoxy benzyle.1R, cis 2,2-dimethyl 3- (2 ', 2'-dibromovinyl) cyclopropane-1 carboxylate of RS α-bromo 3-phenoxy benzyl.

A un mélange de 5,66 g de bromure de l'acide 1R,cis 2,2-diméthyl 3-(2',2'-dibromovinyl)cyclopropane-1-carboxylique et de 3,11 g d'aldéhyde métaphénoxy benzoïque,on ajoute 5 mg de chlorure de. zinc. On note un échauffement et un épaississement du mélange réactionnel. On laisse encore pendant une heure à 20°C et dans des conditions rigoreusement anhydres, on obtient le 1R,cis 2,2-diméthyl 3-(2',2'-dibromovinyl)cyclopropane-1-carboxylate de RS α-bromo 3-phénoxy benzyle.To a mixture of 5.66 g of 1R acid bromide, cis 2,2-dimethyl 3- (2 ', 2'-dibromovinyl) cyclopropane-1-carboxylic acid and 3.11 g of metaphenoxy benzoic aldehyde, 5 mg of chloride are added. zinc. There is heating and thickening of the reaction mixture. It is left for another hour at 20 ° C. and under strictly anhydrous conditions, 1R, cis 2,2-dimethyl 3- (2 ', 2'-dibromovinyl) cyclopropane-1-carboxylate of RS α-bromo 3 is obtained. -phenoxy benzyl.

Spectre Infra-Rouge (chloroforme)Infrared spectrum (chloroform)

Absorption à 1750 cm-1 caractéristique du carboxyle.Absorption at 1750 cm -1 characteristic of the carboxyl.

Spectre de RMN (deutéro chloroforme)NMR spectrum (deutero chloroform)

  • Pics à 1,26-1,33 p.p.m. caractéristiques des hydrogènes des méthyles géminés,Peaks at 1.26-1.33 p.p.m. characteristics of the hydrogens of twin methyls,
  • pics à 1,75-2,16 p.p.m. caractéristiques des hydrogènes du cyclopropyle;peaks at 1.75-2.16 p.p.m. characteristics of the cyclopropyl hydrogens;
  • pics à 6,76-6,88 p.p.m. caractéristiques de l'hydrogène éthylénique;peaks at 6.76-6.88 p.p.m. characteristics of ethylenic hydrogen;
  • pics à 7,0-7,75 p.p.m. caractéristiques des hydrogènes du phényle et du benzyle.peaks at 7.0-7.75 p.p.m. characteristics of the phenyl and benzyl hydrogens.

Le bromure de l'acide 1 R,cis 2,2-diméthyl 3-12',2'-dibromovinyl)cyclopropane-1-carboxylique peut être obtenu de la manière suivante:

  • Dans 60 cm3 de toluène, on dissout 18 g d'acide 1R,cis 2,2-diméthyl 3-(2',2'-dibromovinyl) cyclopropane-1-carboxylique, ajoute 0,2 cm3 de pyridine puis progressivement 6 cm3 de tribromure de phosphore, agite à 20°C pendant 6 jours, sépare par décantation une huile dense qui s'est formée à la partie inférieure du mélange réactionnel, élimine le solvant par distillation sous pression réduite, rectifie le résidu et obtient 14 g de bromure de l'acide 1R,cis 2,2-dimethyl 3-(2',2'-dibromovinyl) cyclopropane-1-carboxylique (Eb. 110°C sous 0,2 mm de mercure).
The acid bromide 1 R, cis 2,2-dimethyl 3-12 ', 2'-dibromovinyl) cyclopropane-1-carboxylic can be obtained in the following way:
  • In 60 cm3 of toluene, 18 g of 1R acid, cis 2,2-dimethyl 3- (2 ', 2'-dibromovinyl) cyclopropane-1-carboxylic acid are dissolved, 0.2 cm3 of pyridine is added and then gradually 6 cm3 of phosphorus tribromide, stirred at 20 ° C for 6 days, separates by decantation a dense oil which has formed at the bottom of the reaction mixture, removes the solvent by distillation under reduced pressure, rectifies the residue and obtains 14 g of bromide 1R acid, cis 2,2-dimethyl 3- (2 ', 2'-dibromovinyl) cyclopropane-1-carboxylic acid (bp 110 ° C under 0.2 mm of mercury).

Spectre Infra-Rouge (chloroforme)Infrared spectrum (chloroform)

Absorption à 1792 cm-1 caractéristique du carboxyle.Absorption at 1792 cm -1 characteristic of the carboxyl.

Spectre de RMN (deutéro chloroforme)NMR spectrum (deutero chloroform)

  • Pics à 1,32-1,36 p.p.m. caractéristiques des hydrogènes des méthyles géminés;Peaks at 1.32-1.36 p.p.m. characteristics of the hydrogens of the twin methyls;
  • pics à 2, 12-2, 26-2,40 p.p.m. caractéristiques de l'hydrogène en position 1 du cyclopropyle;peaks at 2, 12-2, 26-2.40 p.p.m. characteristics of the hydrogen in position 1 of the cyclopropyl;
  • pics à 2,66-2,80 p.p.m. caractéristiques de l'hydrogène en position 3 du cyclopropyle;peaks at 2.66-2.80 p.p.m. characteristics of the hydrogen in position 3 of the cyclopropyl;
  • pics à 6,53-6,66 p.p.m. caractéristiques de l'hydrogène éthylénique.peaks at 6.53-6.66 p.p.m. characteristics of ethylenic hydrogen.
Exemple 6Example 6 1R,trans 2,2-diméthyl 3-(2',2'-dibromovinyl)cyclopropane-1-carboxylate de RS a-chloro 3-phénoxy benzyle.1R, trans 2,2-dimethyl 3- (2 ', 2'-dibromovinyl) cyclopropane-1-carboxylate of RS a-chloro 3-phenoxy benzyl.

Dans un mélange de 6,4 g de chlorure de l'acide 1R,trans 2,2-diméthyl 3-(2',2'-dibromovinyl)cyclopropane-1-carboxylique et de 4 g d'aldéhyde métaphénoxy benzoïque on introduit 10 mg de chlorure de zinc, agite pendant une heure et obtient une solution de 1 R,trans 2,2-diméthyl 3-(2',2'-dibromovinyl)cyclopropane-1-carboxylate de RS a-chloro 3-phénoxy benzyle.10.4 g of 1R acid chloride, trans 2,2-dimethyl 3- (2 ', 2'-dibromovinyl) cyclopropane-1-carboxylic acid and 4 g of benzoic metaphenoxy aldehyde are introduced into 10 mg of zinc chloride, stirred for one hour and obtained a solution of 1 R, trans 2,2-dimethyl 3- (2 ', 2'-dibromovinyl) cyclopropane-1-carboxylate of RS a-chloro 3-phenoxy benzyl.

Exemple 7Example 7 lR,cis 2,2-diméthyl 3-(2',2'-dichlorovinyl)cyclopropane-1-carboxylate de RS α-chloro 3-phénoxy benzyle.1R, cis 2,2-dimethyl 3- (2 ', 2'-dichlorovinyl) cyclopropane-1-carboxylate of RS α-chloro 3-phenoxy benzyl.

Dans un mélange de 4,6 g de chlorure de l'acide 1R,cis 2,2-diméthyl 3-(2',2'-dichlorovinyl)cyclopropane-1-carboxylique et de 4 g de métaphénoxy benzaldéhyde, on introduit 10 mg de chlorure de zinc, agite pendant une heure et obtient une solution de 1 R,cis 2,2-diméthyl 3-(2',2'-dichlorovinyl)cyclopropane-1-carboxylate de RS a-chloro 3-phénoxy benzyle.10 mg of metaphenoxy benzaldehyde are introduced into a mixture of 4.6 g of 1R acid chloride, cis 2,2-dimethyl 3- (2 ', 2'-dichlorovinyl) cyclopropane-1-carboxylic acid and 4 g of metaphenoxy benzaldehyde of zinc chloride, stirred for one hour and obtained a solution of 1 R, cis 2,2-dimethyl 3- (2 ', 2'-dichlorovinyl) cyclopropane-1-carboxylate of RS a-chloro 3-phenoxy benzyl.

Exemple 8Example 8 2,2-diméthyl 3R-(2'-methyl 1'-propényl)cyclopropane-1R-carboxylate de RS α-chloro 3-phénoxy benzyle.2,2-dimethyl 3R- (2'-methyl 1'-propenyl) cyclopropane-1R-carboxylate of RS α-chloro 3-phenoxy benzyl.

Dans un mélange de 1,89 g de chlorure de l'acide 2,2-diméthyl 3R-(2'-méthyl 1'-propényl)cyclopropane-1 R-carboxylique et de 2 g d'aldéhyde métaphénoxy benzylique, on ajoute 10 mg de chlorure de zinc, agite pendant deux heures et 30 minutes et obtient 3,89 g de 2,2-diméthyl 3R-(2'-méthyl 1'-propényl)cyclopropane-1R-carboxylate de RS a-chloro 3-phénoxy benzyle brut.To a mixture of 1.89 g of 2,2-dimethyl 3R- (2'-methyl 1'-propenyl) cyclopropane-1 R-carboxylic acid chloride and 2 g of metaphenoxy benzyl aldehyde, 10 is added. mg of zinc chloride, stirred for two hours and 30 minutes and obtained 3.89 g of 2,2-dimethyl 3R- (2'-methyl 1'-propenyl) cyclopropane-1R-RS carboxylate a-chloro 3-phenoxy raw benzyl.

Exemple 9Example 9 2-(parachlorophényl)2-isopropyl acétate de RS α-chloro 3-phénoxy benzyle.2- (parachlorophenyl) 2-isopropyl acetate of RS α-chloro 3-phenoxy benzyl.

Dans un mélange de 4,7 de chlorure de l'acide 2-(parachlorophényle)2-isopropyl acétique et de 4 g de métaphénoxy benzaldéhyde on introduit 10 mg de chlorure de zinc, agite pendant trois heures à 20°C et obtient une solution de 2-(parachlorophényle)2-isopropyl acétate de RS a-chloro 3-phénoxy benzyle.10 mg of zinc chloride is introduced into a mixture of 4.7 (2- (parachlorophenyl) 2-isopropyl acetic acid chloride and 4 g of metaphenoxy benzaldehyde, stirred for three hours at 20 ° C. and a solution is obtained. of 2- (parachlorophenyl) 2-isopropyl acetate of RS a-chloro 3-phenoxy benzyl.

Exemple 10Example 10 1 R,cis 2.2-diméthyl 3-(2',2'-dibromovinyl)cyclopropane-1-carboxylate de RS a-chloro cinnamyle.1 R, cis 2.2-dimethyl 3- (2 ', 2'-dibromovinyl) cyclopropane-1-carboxylate of RS a-chloro cinnamyle.

Dans un mélange de 4,84 g de chlorure de l'acide 1 R,cis 2,2-diméthyl 3-(2',2'-dibromovinyl)cyclopropane-1-carboxylique et de 2,22 g d'aldehyde cinnamique, on introduit 10 mg de chlorure de zinc, agite pendant une heure à 20°C et obtient 7,06 g de 1 R,cis 2,2-diméthyl 3-(2',2'-dibromovinyl)cyclopropane-1-carboxylate de RS α-chloro cinnamyle brut (F=82°C environ).In a mixture of 4.84 g of 1 R acid chloride, cis 2,2-dimethyl 3- (2 ', 2'-dibromovinyl) cyclopropane-1-carboxylic acid and 2.22 g of cinnamic aldehyde, 10 mg of zinc chloride are introduced, the mixture is stirred for one hour at 20 ° C. and 7.06 g of 1 R, cis 2,2-dimethyl 3- (2 ', 2'-dibromovinyl) cyclopropane-1-carboxylate are obtained. RS α-chloro cinnamyle crude (F = 82 ° C approximately).

Exemple 11Example 11 1R,cis 2,2-diméthyl 3-(2',2'-dibromovinyl)cyclopropane-1-carboxylate de RS a-fluoro 3-phénoxy benzyle.1R, cis 2,2-dimethyl 3- (2 ', 2'-dibromovinyl) cyclopropane-1-carboxylate of RS a-fluoro 3-phenoxy benzyl.

Ce composé peut être obtenu par action du fluorure de l'acide 1R, cis 2,2-diméthyl 3-(2',2'-dibromovinyl) cyclopropane 1-carboxylique avec l'aldéhyde métaphénoxybenzoïque en présence de chlorure de zinc.This compound can be obtained by the action of 1R acid fluoride, cis 2,2-dimethyl 3- (2 ', 2'-dibromovinyl) cyclopropane 1-carboxylic acid with metaphenoxybenzoic aldehyde in the presence of zinc chloride.

Il peut également être obtenu de la manière suivante:

  • Stade A: Fluorure de métaphénoxy benzyle.
    • a) Préparation de la résine inspirée d'un procédé décrit par G. CAINELLI et F. MANESCALCHI (Synthesis 1976 472), 220 g de résine Amberlite A 26, de la firme Rohm et Haas sont lavés par percolation avec 1,5 litre de solution aqueuse N de soude, puis à l'eau à neutralité. La résine humide comportant des groupements OH- est agitée pendant 20 heures à 20°C dans une solution aqueuse d'acide fluorhydrique environ N, puis on essore lave abondamment à l'eau, à l'acétone et à l'éther. La résine est finalement séchée pendant 10 heures à 50°C, sous pression réduite.
    • b) Obtention du fluorure de métaphénoxy benzyle.
It can also be obtained as follows:
  • Stage A: Metaphenoxy benzyl fluoride.
    • a) Preparation of the resin inspired by a process described by G. CAINELLI and F. MANESCALCHI (Synthesis 1976 472), 220 g of Amberlite A 26 resin, from the firm Rohm and Haas are washed by percolation with 1.5 liters of aqueous solution N of sodium hydroxide, then with neutral water. The wet resin comprising OH- groups is stirred for 20 hours at 20 ° C. in an aqueous solution of hydrofluoric acid about N, then it is wrung out thoroughly with water, acetone and ether. The resin is finally dried for 10 hours at 50 ° C, under reduced pressure.
    • b) Obtaining metaphenoxy benzyl fluoride.

On chauffe à 100°C, pendant 20 heures, sous agitation un mélange de 10,5 g de chlorure de méthaphénoxy benzyle, de 150 cm3 de toluène et de 40 g de résine obtenue au paragraphe a).The mixture is heated at 100 ° C., for 20 hours, with stirring, a mixture of 10.5 g of methaphenoxy benzyl chloride, 150 cm 3 of toluene and 40 g of resin obtained in paragraph a).

On élimine la résine par filtration, la lave au chlorure de méthylène, élimine les solvants par distillation sous pression réduite, rectifie le résidu et obtient 5,8 g de fluorure de métaphénoxy benzyle (Eb. 93°C sous 0,05 mm de mercure).The resin is removed by filtration, washed with methylene chloride, the solvents are removed by distillation under reduced pressure, the residue is rectified and 5.8 g of metaphenoxy benzyl fluoride (bp 93 ° C under 0.05 mm of mercury) are obtained. ).

Spectre de RMN (deutéro chloroforme)NMR spectrum (deutero chloroform)

  • Pics à 4,91-5,71 p.p.m. caractéristiques des hydrogènes de -CH2F;Peaks at 4.91-5.71 ppm characteristic of the hydrogens of -CH 2 F;
  • pics à 6,91-7,6 p.p.m. caractéristiques des hydrogènes des noyaux aromatiques.peaks at 6.91-7.6 p.p.m. characteristics of hydrogens in aromatic rings.
  • Stade B: 1-bromofluoro méthyl 3-phénoxy benzène.Stage B: 1-bromofluoro methyl 3-phenoxy benzene.

Dans 20 cm3 de tétrachlorure de carbone, on introduit 2 g de fluorure de métaphénoxy benzyle, 2 g de N-bromosuccinimide et 50 mg d'azoisobutyronitrile, porte le mélange réactionnel au reflux, maintient le reflux pendant une heure, refroidit, élimine la succinimide parfiltration, concentre à sec par distillation sous pression réduite, purifie le résidu par chromatographie sur gel de silice en éluant à l'éther de pétrole (Eb. 35-75°) et obtient 1,8 g de 1-bromofluorométhyl 3-phénoxy benzène.

Figure imgb0050

  • Pics à 6,43-7,75 p.p.m. caractéristiques de l'hydrogène de
    Figure imgb0051
  • pics à 6,91-7,5 p.p.m. caractéristiques des hydrogènes des noyaux aromatiques.
  • Stade C: 1R,cis 2,2-diméthyl 3-(2',2'-dibromovinyl)cycloprop-ane-1-carboxylate de RS α-fluoro 3- phénoxy benzyle.
In 20 cm3 of carbon tetrachloride, 2 g of metaphenoxy benzyl fluoride, 2 g of N-bromosuccinimide and 50 mg of azoisobutyronitrile are introduced, brings the reaction mixture to reflux, maintains reflux for one hour, cools, eliminates the succinimide Parfiltration, concentrated to dryness by distillation under reduced pressure, purifies the residue by chromatography on silica gel, eluting with petroleum ether (Eb. 35-75 °) and obtains 1.8 g of 1-bromofluoromethyl 3-phenoxy benzene .
Figure imgb0050
  • Peaks at 6.43-7.75 ppm characteristic of hydrogen from
    Figure imgb0051
  • peaks at 6.91-7.5 ppm characteristic of hydrogens in aromatic rings.
  • Stage C: 1R, cis 2,2-dimethyl 3- (2 ', 2'-dibromovinyl) cycloprop-ane-1-carboxylate of RS α-fluoro 3- phenoxy benzyl.

Dans 10 cm3 de diméthyl formamide, on introduit 1,19 g de 1-bromo-fluoro méthyl 3-phénoxy benzène, 1,5 g de sel de sodium de l'acide 1 R,cis 2,2-diméthyl 3-(2',2'-dibromovinyl)cyclopropane-1-carboxylique, agite à 20°C pendant 17 heures, verse le mélange réactionnel dans l'eau glacée, extrait au benzène et après traitements habituels, concentre à sec par distillation sous pression réduite. Le résidu'obtenu correspondant au 1R,cis 2,2-diméthyl 3-(2',2'-dibromovinyl)cyclopropane-1-carboxylate de RS α-fluoro 3-phénoxy benzyle brut est formé de deux diastéréoisomères que l'on sépare par chromatographie sur gel de silice, par élution, avec un mélange d'éther de pétrole (Eb. 35°C-75°C) et d'éther éthylique (95/5), on obtient 0,530 g du diastéréoisomère A, F=80°C le plus mobile, 0,700 g de l'autre diastéréoisomère
F=50°C le moins mobile, ainsi que 0,420 g du mélange des deux isomères précédents, soit en tout 1,65 g de 1R,cis 2,2-diméthyl 3-(2',2'-dibromovinyl)cyclopropane-1-carboxylate de RS α-fluoro-3- phénoxy benzyle.1.19 g of 1-bromo-fluoro methyl 3-phenoxy benzene, 1.5 g of sodium salt of 1 R acid, cis 2,2-dimethyl 3- (2 ', 2'-dibromovinyl) cyclopropane-1-carboxylic, stirred at 20 ° C for 17 hours, poured the reaction mixture into ice water, extracted with benzene and after usual treatments, concentrated to dryness by distillation under reduced pressure. The residue obtained corresponding to 1R, cis 2,2-dimethyl 3- (2 ', 2'-dibromovinyl) cyclopropane-1-carboxylate of RS α-fluoro 3-phenoxy benzyl crude is formed of two diastereoisomers which are separated by chromatography on silica gel, by elution, with a mixture of petroleum ether (Eb. 35 ° C-75 ° C) and ethyl ether (95/5), 0.530 g of the diastereoisomer A, F = 80 ° C most mobile, 0.700 g of the other diastereoisomer
M = 50 ° C the less mobile, as well as 0.420 g of the mixture of the two preceding isomers, ie in total 1.65 g of 1R, cis 2,2-dimethyl 3- (2 ', 2'-dibromovinyl) cyclopropane-1 -carboxylate of RS α-fluoro-3-phenoxy benzyl.

L'isomère le plus mobile (F=80°C), isomère A, possède les caractéristiques suivants:

  • Spectre de RMN (deutéro chloroforme)
  • Pics à 1,32-1,35' p.p.m., caractéristiques des hydrogènes des méthyles géminés;
  • pics à 6,8-7,71 p.p.m., caractéristique de l'hydrogène porté par le même carbone que le fluor;
  • pics à 1,85-2,1 p.p.m. caractéristiques des hydrogènes du cyclopropyle,
  • pics à 6,66- p.p.m.-7,83 p.p.m. caractéristiques des hydrogènes des noyaux aromatiques.
Figure imgb0052
 The most mobile isomer (F = 80 ° C), isomer A, has the following characteristics:
  • NMR spectrum (deutero chloroform)
  • Peaks at 1.32-1.35 ppm, characteristic of the hydrogens of the twin methyls;
  • peaks at 6.8-7.71 ppm, characteristic of hydrogen carried by the same carbon as fluorine;
  • peaks at 1.85-2.1 ppm characteristic of cyclopropyl hydrogens,
  • peaks at 6.66 ppm-7.83 ppm characteristic of hydrogens in aromatic rings.
Figure imgb0052

L'isomère le moins mobile (F=50°C), isomère B, posséde les caractéristiques suivantes:

  • Spectre RMN (deutéro chloroforme)
  • Pics à 1,28 p.p.m. caractéristiques des hydrogènes des méthyles géminés,
  • pics à 6,8-7,7 p.p.m. caractéristique de l'hydrogène porté par le même carbone que le fluor; pics à 1,86-2,25 p.p.m. caractéristiques des hydrogènes du cyclopropyle,
  • pics à 6,8-7,6 p.p.m. caractéristiques des hydrogènes des noyaux aromatiques.
Figure imgb0053
 The least mobile isomer (F = 50 ° C), isomer B, has the following characteristics:
  • NMR spectrum (deutero chloroform)
  • Peaks at 1.28 ppm characteristic of hydrogens in twin methyls,
  • peaks at 6.8-7.7 ppm characteristic of hydrogen carried by the same carbon as fluorine; peaks at 1.86-2.25 ppm characteristic of cyclopropyl hydrogens,
  • peaks at 6.8-7.6 ppm characteristic of hydrogens in aromatic rings.
Figure imgb0053

Exemple 12Example 12

1R, trans 2,2-diméthyl 3-(1',2'-dibromo 2',2'-dichloroéthyl) cyclopropane 1-carboxylate de R,S α-chloro 3-phénoxy benzyle.1R, trans 2,2-dimethyl 3- (1 ', 2'-dibromo 2', 2'-dichloroethyl) cyclopropane 1-carboxylate of R, S α-chloro 3-phenoxy benzyl.

On mélange 8 g de 3-phénoxy benzaldéhyde, 15,5 g de chlorure de l'acide (1 R, trans) 2,2-diméthyl 3-(1',2'-dibromo 2',2'-dichloroéthyl) cyclopropane 1-carboxylique, tiédit pour obtenir un liquide homogène, refroidit à 20°C, introduit 0,150 g de chlorure de zinc anhydre, abandonne pendant 17 heures à 20°C, sous agitation et obtient le (1R,trans) 2,2-diméthyl 3-(1',2'-dibromo 2',2'-dichloroéthyl) cyclopropane 1-carboxylate de R,S α-chloro 3-phénoxy benzyle brut.8 g of 3-phenoxy benzaldehyde, 15.5 g of acid chloride (1 R, trans) 2,2-dimethyl are mixed 3- (1 ', 2'-dibromo 2', 2'-dichloroethyl) 1-carboxylic cyclopropane, warm to obtain a homogeneous liquid, cooled to 20 ° C, introduced 0.150 g of anhydrous zinc chloride, left for 17 hours at 20 ° C, with stirring and obtains the (1R, trans) 2,2-dimethyl 3- (1 ', 2'-dibromo 2', 2'-dichloroethyl) cyclopropane 1-carboxylate of R, S α-chloro 3- crude phenoxy benzyl.

Le spectre infrarouge de ce produit fait apparaître une absorption caractéristique à 1750 cm-1 (caractéristique du carbonyle).The infrared spectrum of this product shows a characteristic absorption at 1750 cm -1 (characteristic of carbonyl).

Le spectre de RMN permet de constater l'absence de proton aldéhydique.The NMR spectrum shows the absence of aldehyde proton.

Exemple 13Example 13 1R,cis 2,2-diméthyl 3-(2',2'-dibromovinyl)cyclopropane-1-carboxylate de RS α-cyano 3-phénoxy benzyle.1R, cis 2,2-dimethyl 3- (2 ', 2'-dibromovinyl) cyclopropane-1-carboxylate of RS α-cyano 3-phenoxy benzyl.

Dans 50 cm3 d'acétonitrile anhydre, on dissout 5,5 g du dérivé a-chloré brut obtenu à l'exemple 1, 0,8 g de cyanure de potassium anhydre, agite pendant 17 heures à 20°C, ajoute de l'eau, extrait au benzène et après les traitements habituels recueille 5,6 g de produit brut que l'on purifie par chromatographie sur gel de silice' en éluant avec un mélange d'éther de pétrole (Eb. 35-75°C) et d'éther éthylique (9/1) et obtient 4,3 g de 1 R cis 2,2-diméthyl 3-(2',2'-dibromovinyl)cyclopropane-1-carboxylate de RS a-cyano 3-phénoxy benzyle.5.5 g of the crude α-chlorine derivative obtained in Example 1 are dissolved in 50 cm 3 of anhydrous acetonitrile, 0.8 g of anhydrous potassium cyanide, stirred for 17 hours at 20 ° C., added with water, benzene extract and after the usual treatments collects 5.6 g of crude product which is purified by chromatography on silica gel 'eluting with a mixture of petroleum ether (bp 35-75 ° C) and ethyl ether (9/1) and obtains 4.3 g of 1 R cis 2,2-dimethyl 3- (2 ', 2'-dibromovinyl) cyclopropane-1-carboxylate of RS a-cyano 3-phenoxy benzyl.

Exemple 14Example 14 1R, cis 2,2-diméthyl 3-(2'2'-dibromovinyl) cyclopropane 1-carboxylate de RS a-cyano 3-phénoxy benzyle.1R, cis 2,2-dimethyl 3- (2'2'-dibromovinyl) cyclopropane 1-carboxylate of RS a-cyano 3-phenoxy benzyl.

De manière analogue à celle de l'exemple 13, au départ du dérivé α-bromé obtenu à l'exemple 5, on obtient le 1 R, cis 2,2-diméthyl 3-(2',2'-dibromovinyl) cyclopropane 1-carboxylate de de RS a-cyano 3-phénoxy benzyle.Analogously to that of Example 13, starting from the α-brominated derivative obtained in Example 5, the 1 R, cis 2,2-dimethyl 3- (2 ', 2'-dibromovinyl) cyclopropane 1 is obtained -carboxylate of RS a-cyano 3-phenoxy benzyl.

Exemple 15Example 15 1R,cis 2,2-diméthyl 3-(2',2'-dibromovinyl)cyclopropane-1-carboxylate de RS α-cyano 3-phénoxy benzyle.1R, cis 2,2-dimethyl 3- (2 ', 2'-dibromovinyl) cyclopropane-1-carboxylate of RS α-cyano 3-phenoxy benzyl.

Dans 15 cm3 d'acétonitrile, on dissout 1,17 g de dérivé a-fluoré brut obtenu à l'exemple 11; ajoute 0,2 g de cyanure de potassium, agite pendant 17 heures à 20°C, chromatographie le résidu sur gel de silice en éluant avec un mélange d'éther de pétrole et d'éther (9/1 ) et obtient 1 g de 1 R,cis 2,2-diméthyl 3-(2',2'-dibromovinyl)cyclopropane-1R-carboxylate de RS α-cyano 3-phénoxy benzyle.1.17 g of crude a-fluorinated derivative obtained in Example 11 are dissolved in 15 cm 3 of acetonitrile; add 0.2 g of potassium cyanide, stir for 17 hours at 20 ° C, chromatograph the residue on silica gel, eluting with a mixture of petroleum ether and ether (9/1) and obtain 1 g of 1 R, cis 2,2-dimethyl 3- (2 ', 2'-dibromovinyl) cyclopropane-1R-carboxylate of RS α-cyano 3-phenoxy benzyl.

Exemple 16Example 16 1R,trans 2,2-diméthyl 3-(2',2'-dibromovinyl)cyclopropane-1-carboxylate de RS α-cyano 3-phénoxy benzyle.1R, trans 2,2-dimethyl 3- (2 ', 2'-dibromovinyl) cyclopropane-1-carboxylate of RS α-cyano 3-phenoxy benzyl.

Dans la solution de 1R.trans 2.2-diméthyl 3-(2'.2'-dibromovinyl)cyclopropane-1-carboxylate de RS a-chloro 3-phénoxy benzyle obtenu à l'exemple 6 on introduit 90 cm3 d'acétonitrile, 1,5 g de cyanure de potassium, agite pendant 16 heures, ajoute de l'eau, extrait au benzène, puis après les traitements habituels, concentre à sec par distillation sous pression réduite.90 cm3 of acetonitrile are introduced into the solution of 1R.trans 2.2-dimethyl 3- (2'.2'-dibromovinyl) cyclopropane-1-carboxylate of RS a-chloro 3-phenoxy benzyl obtained in Example 6. , 5 g of potassium cyanide, stirred for 16 hours, added water, extracted with benzene, then after the usual treatments, concentrated to dryness by distillation under reduced pressure.

Le résidu est chromatographié sur gel de silice en éluant par un mélange de benzène et de cyclohexane (6/4) et l'on obtient 7,5 g de 1 R, trans 2,2-diméthyl 3-(2',2'-dibromovinyl)cyclopropane 1 - carboxylate de RS a-cyano 3-phénoxy benzyle.The residue is chromatographed on silica gel, eluting with a mixture of benzene and cyclohexane (6/4) and 7.5 g of 1 R, trans 2,2-dimethyl 3- (2 ', 2') are obtained. -dibromovinyl) cyclopropane 1 - RS a-cyano 3-phenoxy benzyl carboxylate.

Exemple 17Example 17 1R,cis 2,2-diméthyl 3-(2',2'-dichlorovinyl)cyclopropane-1-carboxylate de RS a-cyano 3-phénoxy benzyle.1R, cis 2,2-dimethyl 3- (2 ', 2'-dichlorovinyl) cyclopropane-1-carboxylate of RS a-cyano 3-phenoxy benzyl.

A une solution de 1 R,cis 2,2-diméthyl 3-(2',2'-dichlorovinyl)cyclopropane-1-carboxylate de RS α-chloro 3-phénoxy benzyle obtenu à l'exemple 7, on ajoute 80 cm3 d'acétonitrile, 1,5 g de cyanure de potassium, agite pendant 17 heures, ajoute de l'eau, extrait au benzène et après les traitements classiques, concentre à sec par distillation sous pression réduite, chromatographie le résidu sur gel de silice en éluant par un mélange de benzène et de cyclohexane (6/4) et obtient: 6,4 g de 1 R,cis 2,2-diméthyl 3-(2',2'-dichlorovinyl)cyclopropane-1-carboxylate de RS α-cyano 3-phénoxy benzyle.To a solution of 1 R, cis 2,2-dimethyl 3- (2 ', 2'-dichlorovinyl) cyclopropane-1-carboxylate of RS α-chloro 3-phenoxy benzyl obtained in Example 7, 80 cm3 d are added. acetonitrile, 1.5 g of potassium cyanide, stirred for 17 hours, add water, extract with benzene and after conventional treatments, concentrate to dryness by distillation under reduced pressure, chromatograph the residue on silica gel, eluting with a mixture of benzene and cyclohexane (6/4) and obtains: 6.4 g of 1 R, cis 2,2-dimethyl 3- (2 ', 2'-dichlorovinyl) cyclopropane-1-carboxylate of RS α- cyano 3-phenoxy benzyl.

Exemple 18Example 18 2,2-diméthyl 3R-(2'-méthyl 1'-propényl)cyclopropane-1R-carboxylate de RS α-cyano 3-phénoxy benzyle.2,2-dimethyl 3R- (2'-methyl 1'-propenyl) cyclopropane-1R-carboxylate of RS α-cyano 3-phenoxy benzyl.

Dans 50 cm3 d'acétonitrile, on dissout 3,09 g de 2,2-diméthyl 3R-(2'-méthyl 1'-propényl)cyclopropane-1 R-carboxylate de RS a-chloro 3-phénoxy benzyle brut obtenu à l'exemple 8, ajoute 1,1 g de cyanure de potassium, agite pendant 48 heures, ajoute de la glace, extrait au benzène, sèche sur sulfate de magnésium, filtre, et concentre à sec par distillation sous pression réduite. Le résidu (3,96 g) est chromatographié sur gel de silice en éluant par un mélange de cyclohexane et d'acétate d'éthyle (9/1) et obtient 0,48 g de 2,2-diméthyl 3R-(2'-méthyl 1'-propényl)cyclopropane-1R-carboxylate de RS a-cyano 3-phénoxy benzyle.In 50 cm3 of acetonitrile, 3.09 g of 2,2-dimethyl 3R- (2'-methyl 1'-propenyl) cyclopropane-1 R-carboxylate of RS a-chloro 3-phenoxy benzyl obtained at l are dissolved. Example 8, add 1.1 g of potassium cyanide, stir for 48 hours, add ice, extract with benzene, dry over magnesium sulfate, filter, and concentrate to dryness by distillation under reduced pressure. The residue (3.96 g) is chromatographed on silica gel, eluting with a mixture of cyclohexane and ethyl acetate (9/1) and gives 0.48 g of 2,2-dimethyl 3R- (2 ' -methyl 1'-propenyl) cyclopropane-1R-carboxylate of RS a-cyano 3-phenoxy benzyl.

Spectre Infra-Rouge (chloroforme)Infrared spectrum (chloroform)

  • Absorption à 1733 cm-1 caractéristiques du carboxyle;Absorption at 1733 cm -1 characteristics of the carboxyl;
  • absorptions à 1487-1587 cm-1, caractéristiques des noyaux aromatiques.absorptions at 1487-1587 cm -1 , characteristic of aromatic nuclei.
Exemple 19Example 19 2-(parachlorophényl)2-isopropyl acétate de RS α-cyano 3-phénoxy benzyle.2- (parachlorophenyl) 2-isopropyl acetate of RS α-cyano 3-phenoxy benzyl.

A la solution de 2-(parachlorophényl)2-isopropyl acétate de RS α-chloro 3-phénoxy benzyle obtenu à l'exemple 9, on ajoute 80 cm3 d'acétonitrile, 1,5 g de cyanure de potassium, agite pendant 72 heures à 20°C, ajoute de l'éther, élimine par filtration l'insoluble formé, concentre le filtrat à sec par distillation sous pression réduite, chromatographie le résidu sur gel de silice en éluant par un mélange de cyclohexane et d'acétone (95/5) et obtient 6,5 g de 2-(parachlorophényl)2-isopropyl acétate de RS α-cyano 3-phénoxy benzyle.To the solution of 2- (parachlorophenyl) 2-isopropyl acetate of RS α-chloro 3-phenoxy benzyl obtained in Example 9, 80 cm3 of acetonitrile, 1.5 g of potassium cyanide, are added and stirred for 72 hours at 20 ° C, add ether, filter out the insoluble material formed, concentrate the filtrate to dryness by distillation under reduced pressure, chromatograph the residue on silica gel, eluting with a mixture of cyclohexane and acetone (95 / 5) and obtains 6.5 g of 2- (parachlorophenyl) 2-isopropyl acetate of RS α-cyano 3-phenoxy benzyl.

Exemple 20Example 20 1R, cis 2,2-diméthyl 3-(2',2'-dibromovinyl) cyclopropane 1-carboxylate de RS α-cyano cinnamyle1R, cis 2,2-dimethyl 3- (2 ', 2'-dibromovinyl) cyclopropane RS 1-carboxylate α-cyano cinnamyl

A 4,76 g de 1R, cis 2,2-diméthyl 3-(2',2'-dibromovinyl) cyclopropane 1-carboxylate de RS α-chloro cinnamyle brut obtenu à l'exemple 10 dans 75 cm3 d'acétonitrile, on ajoute 1,5 g de cyanure de potassium, agite pendant 42 heures, ajoute de la glace, extrait au benzène, lave à l'eau, sèche sur sulfate de magnésium, filtre et concentre à sec par distillation sous pression réduite. Les 5,3 g de résidu sont chromatographiés sur gel silice, en éluant par un mélange de cyclohexane et d'acétate d'éthyle (9/1 ) et on obtient 1,76 g de 1 R,cis 2,2-diméthyl 3-(2',2'-dibromovinyl)cyclopropane-1-carboxylate de RS α-cyano cinnamyle.

Figure imgb0054
At 4.76 g of 1R, cis 2,2-dimethyl 3- (2 ', 2'-dibromovinyl) cyclopropane 1-carboxylate of RS α-chloro cinnamyl crude obtained in Example 10 in 75 cm3 of acetonitrile, we add 1.5 g of potassium cyanide, stir for 42 hours, add ice, extract with benzene, wash with water, dry over magnesium sulfate, filter and concentrate to dryness by distillation under reduced pressure. 5.3 g of residue are chromatographed on silica gel, eluting with a mixture of cyclohexane and ethyl acetate (9/1) and 1.76 g of 1 R, cis 2.2-dimethyl 3 are obtained. - (2 ', 2'-dibromovinyl) cyclopropane-1-carboxylate of RS α-cyano cinnamyl.
Figure imgb0054

Exemple 21Example 21 (1 R,trans) 2,2-diméthyl 3-(1',2'-dibromo 2',2'-dichloroéthyl) cyclopropane 1-carboxylate de (R) α-cyano 3-phénoxy benzyle et (1R, trans) 2,2-diméthyl 3-(1',2'-dibromo 2',2'-dichloroéthyl) cyclopropane 1-carboxylate de (S) α-cyano 3-phénoxy benzyle.(1 R, trans) 2,2-dimethyl 3- (1 ', 2'-dibromo 2', 2'-dichloroethyl) cyclopropane 1-carboxylate of (R) α-cyano 3-phenoxy benzyl and (1R, trans) 2,2-dimethyl 3- (1 ', 2'-dibromo 2', 2'-dichloroethyl) cyclopropane 1-carboxylate of (S) α-cyano 3-phenoxy benzyl.

A 17,8 g de (1R, trans) 2,2-diméthyl 3-(1',2'-dibromo 2',2'-dichloroéthyl) cyclopropane 1-carboxylate de R,S α-chloro 3-phénoxy benzyle brut, obtenu à l'exemple 12, dissous dans 200 cm3 de benzène, on ajoute 2 g de cyanure de potassium, laisse pendant 50 heures à 20°C, sous agitation, dilue à l'eau, extrait au benzène, concentre à sec, chromatographie le résidu sur gel de silice en éluant avec un mélange d'éther et d'éther de pétrole (1/9) et isole 0,63 g de (1R,trans) 2,2-diméthyl 3-(1',2'-dibromo 2',2'-dichloroéthyl) cyclopropane 1-carboxylate de (R) α-cyano 3-phénoxy benzyle (composé A), puis 1,13 g de (1R,trans) 2,2-diméthyl 3-(1',2'-dibromo2',2'-dichloroéthyl)cyclopropane 1-carboxylate de (S).α-cyano 3-phénoxy benzyle (composé B).A 17.8 g of (1R, trans) 2,2-dimethyl 3- (1 ', 2'-dibromo 2', 2'-dichloroethyl) cyclopropane 1-carboxylate of R, S α-chloro 3-phenoxy benzyl benzyl , obtained in Example 12, dissolved in 200 cm3 of benzene, 2 g of potassium cyanide are added, left for 50 hours at 20 ° C., with stirring, diluted with water, extracted with benzene, concentrated to dryness, chromatograph the residue on silica gel, eluting with a mixture of ether and petroleum ether (1/9) and isolate 0.63 g of (1R, trans) 2,2-dimethyl 3- (1 ', 2 '-dibromo 2', 2'-dichloroethyl) cyclopropane 1-carboxylate of (R) α-cyano 3-phenoxy benzyl (compound A), then 1.13 g of (1R, trans) 2,2-dimethyl 3- ( 1 ', 2'-dibromo2', 2'-dichloroethyl) cyclopropane 1-carboxylate of (S) .α-cyano 3-phenoxy benzyl (compound B).

Le spectre de R.M.N. du composé A présente les caractéristiques suivantes (deuterochloroforme):

  • Pics à 1,32-1,35 p.p.m. caractéristiques des hydrogènes des méthyles en position 2 du cyclopropyle;
  • Pics à 4,18 et 4,35 p.p.m. et 4,35 et 4,53 p.p.m. caractéristiques de l'hydrogène en position l' de la chaîne latérale éthylique;
  • Pics à 6,37 p.p.m., caractéristique de l'hydrogène porté par le même carbone que le groupement nitrile.
The NMR spectrum of compound A has the following characteristics (deuterochloroform):
  • Peaks at 1.32-1.35 ppm characteristic of the methyl hydrogens in position 2 of the cyclopropyl;
  • Peaks at 4.18 and 4.35 ppm and 4.35 and 4.53 ppm characteristic of hydrogen in position l 'of the ethyl side chain;
  • Peaks at 6.37 ppm, characteristic of hydrogen carried by the same carbon as the nitrile group.

Le spectre de R.M.N. du composé B présente les caractéristiques suivantes (deuterochloroforme):

  • Pics à 1,2-1,25-1,32 p.p.m. correspondant aux hydrogènes des méthyles en position 2 du cyclopropyle;
  • Pics à 4,21-4,38-4,37-4,53 p.p.m. attribués au proton en position 1' de la chaîne latérale éthylique;
  • Pic à 6,42 p.p.m. attribué au proton benzylique.
The NMR spectrum of compound B has the following characteristics (deuterochloroform):
  • Peaks at 1.2-1.25-25.32 ppm corresponding to the methyl hydrogens in position 2 of the cyclopropyl;
  • Peaks at 4.21-4.38-4.37-4.53 ppm attributed to the proton in position 1 'of the ethyl side chain;
  • Peak at 6.42 ppm attributed to the benzyl proton.

Exemple 22Example 22 Exemple de composition insecticideExample of insecticide composition

On prépare un concentré émulsifiable en mélangeant intimement:

  • -isomère A du 1R,cis 2,2-diméthyl 3-(2',2'-dibromovinyl) cyclopropane-1-carboxylate d'α-fluoro 3-phénoxy benzyle: 1 g
  • -Tween 80, 20 g
  • -Topanol A: 0,1 g
  • -xylène: 78,9 g
An emulsifiable concentrate is prepared by intimately mixing:
  • -isomer A of 1R, cis 2,2-dimethyl 3- (2 ', 2'-dibromovinyl) cyclopropane-1-carboxylate of α-fluoro 3-phenoxy benzyl: 1 g
  • - Tween 80, 20 g
  • -Topanol A: 0.1 g
  • -xylene: 78.9 g

Etude de l'activité insecticide de l'isomère B du 1R,cis 2,2-diméthyl 3-(2',2'-dibromovinyl)cyclo-, propane-1-carboxylate d'α-fluoro 3-phénoxy benzyle.Study of the insecticidal activity of the B isomer of 1R, cis 2,2-dimethyl 3- (2 ', 2'-dibromovinyl) cyclo-, propane-1-carboxylate of α-fluoro 3-phenoxy benzyl.

Effet létal sur mouche domestique:

  • Les insectes tests sont des mouches domestiques de sexes mélangés. On opère par application topique de 1 µl de solution acétonique sur le thorax dorsal des insectes. On utilise 50 individus par traitement. On effectue le contrôle de mortalité vingt-quatre heures après traitement.
Lethal effect on houseflies:
  • The test insects are houseflies of mixed sexes. We operate by topical application of 1 µl of acetone solution on the dorsal thorax of insects. 50 individuals are used per treatment. The mortality check is carried out twenty-four hours after treatment.

On effectue une série d'essais sans agent de synergie et une série d'essais avec synergie par le butoxyde de pipéronyle dans la proportion 10 parties de pipéronyle butoxyde pour 1 partie de produit à tester. On effectue le contrôle de mortalité vingt-quatre heures après traitement.A series of tests without synergistic agent and a series of tests with synergism are carried out with piperonyl butoxide in the proportion 10 parts of piperonyl butoxide for 1 part of product to be tested. The mortality check is carried out twenty-four hours after treatment.

Les résultats expérimentaux obtenus, résumés dans le tableau suivant, sont exprimés en DL50 (dose létale 50) en nanogrammes par insecte.

Figure imgb0055
The experimental results obtained, summarized in the following table, are expressed in LD50 (lethal dose 50) in nanograms per insect.
Figure imgb0055

Claims (23)

1. In all their stereoisomeric forms or in the form of mixtures of stereoisomers, the compounds of general formula IA:
Figure imgb0145
in which:
-X represents a fluorine, chlorine or bromine atom,
-R1 represents:
either a group R1':
Figure imgb0146
in which:
either Y1 and Y2 are identical and represent a methyl radical,
or Y1 represents a hydrogen atom and Y2 represents a group Y2':
Figure imgb0147
or Y1 represents a hydrogen atom and Y2 represents a group:
Figure imgb0148
Y3 and Y4, being identical or different, representing a fluorine, chlorine or bromine atom or Y3 and Y4, being identical or different, representing a methyl radical or a hydrogen atom, the group R1' corresponding, in the case in which Y2 represents a group:
Figure imgb0149
to a racemic or optically-active acid residue of cis or trans structure, or to a mixture of residues of acid of cis structure and of acid of trans structure, or a group R1":
Figure imgb0150
in which Z represents a hydrogen atom, a fluorine, chlorine or bromine atom, a straight or branched alkyl radical containing from 1 to 4 carbon atoms or a straight or branched alkyloxy radical containing from 1 to 4 carbon atoms, the group R," corresponding to a racemic or optically-active acid residue, and
-R2 represents, in the case in which Y2 is different from Y2':
either a residue selected from the following groups:
Figure imgb0151
Figure imgb0152
or the residue
Figure imgb0153
in which A represents either a group:
Figure imgb0154
or a group:
Figure imgb0155
or a group:
Figure imgb0156
or a group:
Figure imgb0157
or a group:
Figure imgb0158
or R2 represents, in the case in which Y2 represents a group Y2', the residue
Figure imgb0159
in which A represents a group
Figure imgb0160
2. In all their stereoisomeric forms, the compounds according to Claim 1, of general formula I:
Figure imgb0161
in which R2 and X are defined as in Claim 1 and R represents:
either a group R':
Figure imgb0162
in which:
either Y1 and Y2 are identical and represent a methyl radical,
or Y1 represents a hydrogen atom and Y2 represents a group:
Figure imgb0163
Y3 and Y4, being identical or different, representing a fluorine, chlorine or bromine atom, or Y3 and Y4, being identical or different, representing a methyl radical or a hydrogen atom, the group R1' corresponding, in the case in which Y2 represents a group:
Figure imgb0164
to a racemic or optically-active acid residue of cis or trans structure or to a mixture of residues of acid of cis structure and of acid of trans structure,
- or a group R1" as defined in Claim 1.
3. The compounds of formula I, according to Claim 2, containing a group R' in which Y, represents a hydrogen atom and Y2 represents a group:
Figure imgb0165
4. The compounds of formula I, according to Claim 2, in which R2 represents a group:
Figure imgb0166
A having as value:
Figure imgb0167
5. The compounds of formula I, according to Claim 2, in which X represents a fluorine atom.
6. The compounds of formula I, according to one of Claims 2 or 4, in which R2 represents a group:
Figure imgb0168
A having as value:
Figure imgb0169
and in which X represents a fluorine or bromine atom.
7. The compounds of formula I, according to Claim 2, in which X represents a chlorine atom.
8. The compounds of general formula I, according to any one of Claims 2 or 4, of which the names are as follows:
-RS α-chloro 3-phenoxy benzyl 1R, cis 2,2-dimethyl 3-(2',2'-dibromovinyl) cyclopropane-1-carboxylate,
-RS α-fluoro 3-phenoxy benzyl 1R, cis 2,2-dimethyl 3-(2',2'-dibromovinyl) cyclopropane-1-carboxylate,
-RS α-chloro 3-phenoxy benzyl 1R, cis 2,2-dimethyl 3-(2',2'-dichlorovinyl) cyclopropane-1-carboxylate and
-RS α-chloro 3-phenoxy benzyl 2-(parachlorophenyl) 2-isopropyl acetate.
9. The following compound of general formula IA:
-R,S α-chloro 3-phenoxy benzyl 1R, trans 2,2-dimethyl 3-(1',2'-dibromo 2',2'-dichloroethyl) cyclopropane-1-carboxylate.
10. Process for preparing the compounds of general formula IA, as defined in Claim 1, characterised in that, in the presence of an acid catalyst, an acid halide of general formula II:
Figure imgb0170
in which X and R, keep the meanings of Claim 1, is reacted with an aldehyde of general formula III:
Figure imgb0171
in which R2 keeps the meanings of Claim 1.
11. Process for preparing, according to Claim 10, the compounds of general formula I, as defined in Claim 2, characterised in that to start with an acid halide of general formula IIA:
Figure imgb0172
in which X and R are as defined as in Claim 2, is used.
12. Preparation process according to Claim 10 or 11, characterised in that the catalyst is either a Lewis acid such as zinc chloride, aluminium chloride or ferric chloride, or a protonic acid such as paratoluene sulphonic acid or oleum.
13. Process for preparing the compounds of general formula I, as defined in Claim 2, in which X represents a fluorine atom and in which R2 represents either a residue:
Figure imgb0173
or a residue:
Figure imgb0174
in which A represents a group:
Figure imgb0175
a group:
Figure imgb0176
or a group:
Figure imgb0177
characterised in that a quaternary ammonium fluoride fixed on a resin is reacted with a chloride Z, either of formula:
Figure imgb0178
or of formula:
Figure imgb0179
or of formula:
Figure imgb0180
or of formula
Figure imgb0181
the corresponding resultant fluoride Z2 is subjected, in the presence of azoisobutyronitrile, to the action of N-bromo succinimide to obtain a mixed brominated and fluorinated derivative Z3 either of formula:
Figure imgb0182
or of formula:
Figure imgb0183
or of formula
Figure imgb0184
or of formula:
Figure imgb0185
then this compound is reacted with an alkaline salt of general formula IV:
Figure imgb0186
in which R keeps the meanings of Claim 2 and M represents an ion derived from an alkali metal.
14. Use of the compounds of formula IA, as defined in Claim 1, in all their stereoisomeric forms or in the form of mixtures of stereoisomers, in the preparation, in the corresponding stereoisomeric forms, of the compounds of general formula IB:
Figure imgb0187
in which R1 and R2 are defined as in Claim 1, a use characterised in that a compound generating CN- ions is reacted with a compound of general formula IA:
Figure imgb0188
as defined in Claim 1, the resultant compounds of formula IB being in the stereoisomeric forms corresponding to the stereoisomeric forms of the compounds IA used.
15. Use according to Claim 14 of the compounds of formula I, as defined in Claim 2, in all their stereoisomeric forms, in the preparation, in the corresponding stereoisomeric forms, of the compounds of formula IC:
Figure imgb0189
in which R and R2 are defined as in Claim 2, a use characterised in that a compound generating CN- ions is reacted with a compound of general formula I.
16. Use according to Claim 14 or 15, characterised in that, in the formula IA or I, X represents a fluorine or chlorine atom.
17. Use according to Claim 14 or 15, characterised in that the condensation with the agent generating CN- ions is carried out in an anhydrous organic solvent selected from the group constituted by acetonitrile and dimethylformamide.
18. Use according to Claim 14 or 15, characterised in that the agent generating CN- ions is an alkali cyanide.
19. Use, according to any one of Claims 15 to 18, in the preparation of RS a-cyano 3-phenoxy benzyl 1 R, cis 2,2-dimethyl 3-(2',2'-dibromovinyl) cyclopropane-1-carboxylate, characterised in that the compound of formula I used is RS a-chloro 3-phenoxy benzyl 1 R, cis 2,2-dimethyl 3-(2',2'-dibromovinyl) cyclopropane-1-carboxylate.
20. Use, according to any one of Claims 15 to 18, in the preparation of RS a-cyano 3-phenoxy benzyl 1R, cis 2,2-dimethyl 3-(2',2'-dibromovinyl) cyclopropane-1-carboxylate, characterised in that the compound of formula I used is RS a-fluoro 3-phenoxy benzyl 1R, cis 2,2-dimethyl 3-(2',2'-dibromovinyl) cyclopropane-1-carboxylate.
21. Use, according to any one of Claims 15 to 18, in the preparation of RS a-cyano 3-phenoxy benzyl 1R, cis 2,2-dimethyl 3-(2',2'-dichlorovinyl) cyclopropane-1-carboxylate, characterised in that the compound of formula I used is RS a-chloro 3-phenoxy benzyl 1 R, cis 2,2-dimethyl 3-(2',2'-dichlorovinyl) cyclopropane-1-carboxylate.
22. Use, according to any one of Claims 15 to 18, in the preparation of RS a-cyano 3-phenoxy benzyl 2-parachlorophenyl 2-isopropyl acetate, characterised in that the compound of formula I used is RS α-chloro 3-phenoxy benzyl 2-parachlorophenyl 2-isopropyl acetate.
23. Use, according to any one of Claims 14 and 16 to 18, in the preparation of RS a-cyano 3-phenoxy benzyl 1R, trans 2,2-dimethyl 3-(1',2'-dibromo 2',2'-dichloroethyl) cyclopropane-1-carboxylate, characterised in that the compound IA used is RS a-chloro 3-phenoxy benzyl 1 R, trans 2,2-dimethyl 3-(1',2'-dibromo 2',2'-dichloroethyl) cyclopropane-1-carboxylate or RS α-fluoro 3-phenoxy benzyl 1R, trans 2,2-dimethyl 3-(1',2'-dibromo 2',2'-dichloroethyl) cyclopropane-1-carboxylate.
EP78400142A 1977-10-27 1978-10-20 Esters of alpha-halogenated alcohols, method of preparation and application to the synthesis of esters of alpha-cyano substituted alcohols Expired EP0001944B1 (en)

Applications Claiming Priority (8)

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FR7732415A FR2407200A1 (en) 1977-10-27 1977-10-27 Insecticidal ester(s) of alpha-halogenated alcohol(s) - useful in prepn. of insecticidal corresp. cyano-ester(s)
FR7732415 1977-10-27
FR7732414A FR2424249A1 (en) 1977-10-27 1977-10-27 Insecticidal ester(s) of alpha-halogenated alcohol(s) - useful in prepn. of insecticidal corresp. cyano-ester(s)
FR7732414 1977-10-27
FR7821811 1978-07-24
FR7821811A FR2432011A2 (en) 1978-07-24 1978-07-24 Insecticidal ester(s) of alpha-halogenated alcohol(s) - useful in prepn. of insecticidal corresp. cyano-ester(s)
FR7821812A FR2432016A2 (en) 1978-07-24 1978-07-24 Insecticidal ester(s) of alpha-halogenated alcohol(s) - useful in prepn. of insecticidal corresp. cyano-ester(s)
FR7821812 1978-07-24

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US4360689A (en) * 1980-05-12 1982-11-23 Shell Oil Company α-Halobenzyl esters
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US6986898B1 (en) * 1999-06-28 2006-01-17 Ecosmart Technologies, Inc. Synergistic and residual pesticidal compositions containing plant essential oils with enzyme inhibitors

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